Synthesis and Characterization of New Low-Valent Silicon, … · 2017. 10. 26. · Synthesis and...

Synthesis and Characterization of New Low-Valent

Silicon Germanium and Tin Compounds

vorgelegt von

Dipl Chem

Wenyuan Wang

aus Nei Mongol (China)

Von der Fakultaumlt II ndash Mathematik und Naturwissenschaften

der Technischen Universitaumlt Berlin

Institut fuumlr Chemie

zur Erlangung des akademischen Grades

Doktor der Naturwissenschaften

- Dr rer nat -

genehmigte Dissertation

Promotionsausschuss

Vorsitzender Prof Dr Peter Hildebrandt (TU Berlin)

1 Gutachter Prof Dr Matthias Driess (TU Berlin)

2 Gutachter Prof Dr Thomas Braun (HU Berlin)

Tag der wissenschaftlichen Aussprache 31-10-2012

Berlin 2012

D 83

DISSERTATION

by

Dipl Chemiker

Wenyuan Wang

from Nei Mongol (China)

Die vorliegende Arbeit entstand in der Zeit von Feb 2008 bis Jul 2012 unter der

Betreuung von Prof Dr Matthias Driess am Institut fuumlr Chemie der Technischen

Universitaumlt Berlin

Von Herzen kommend gilt mein Dank meinem verehrten Lehrer

Herrn Professor Dr Matthias Drieszlig

fuumlr die Aufnahme in seinen Arbeitskreis fuumlr seine engagierte Unterstuumltzung

und fuumlr die Forschungsfreiheit

My heartfelt thanks go out to

Prof Dr Thomas Braun for his acceptance of the second commentator ship

Prof Dr Peter Hildebrandt for his acceptance of the chairman

Prof Dr Shigeyoshi Inoue and Prof Dr Christoph van Wuumlllen for DFT calculations

and composition assistance during the course of my PhD work and Dr Stephan

Enthaler for the investigation of the catalytic activity

Dr Shenglai Yao Dr Carsten Praesang Dr Andreas Bruumlck Dr Anne Adams Robert

Adams Ms Marianna Tsaroucha Mr Gengwen Tan Mr Daniel Gallego and Mr

Paul Ensle for useful discussions synthetic suggestions composition and

modification assistance during the course of my PhD work

My laboratory coworkers Mr Stefan Schutte for creating a wonderful lab atmosphere

and Ms Paula Nixdorf Dr Elisabeth Irran for X-ray crystal structure determinations

and solutions Dr Jan-Dirk Epping Dr Heinz-Juumlrgen Kroth and Mr Manfred

Dettlaff for NMR measurements Ms Sigrid Imme for CHN and IR measurements

Mr Robert Rudolph for the measurements of cyclic voltammetry

Ms Andrea Rahmel and all members of my work group for their hail-fellow help

friendship and years of harmonious work together and for their acting as guides in

my living and discovery in all things in Germany

I sincerely thank my parents my wife Xiaoxia Zhao and Prof GuoXingBaTu for

selfless support and encouragement of my study in Germany

This work was supported by the Deutsche Forschungsgemeinschaft (DFG) and the

Cluster of Excellence ldquoUnifying Concepts in Catalysisrdquo (Unicat)

Table of contents

i

TABLE OF CONTENTS

1 INTRODUCTION 1

11 The significance of low-valent group 14 compounds 1

12 Heavier carbene analogues of group 14 elements 5

13 Bis-metallylenes and metallylenes with several EII cores 8

14 Coordination chemistry of chelating metallylene ligands 16

2 MOTIVATION 21

3 RESULTS AND DISCUSSION 23

31 Synthesis of Ge Sn carbene analogues and their derivates 23

311 Isolation of the first germylene anion salt 3 and germylene amide 4 23

312 Reduction of (nacnac)GeCl3 2 with KC8 28

313 DFT calculations and aromaticity of 3 and 5 30

314 Synthesis of asymmetric substituted bis-germylene 6 34

315 Synthesis of the first germylene-stannylene 8 35

316 Molecular structures of bis-germylene 6 and germylene-stannylene 8 36

317 DFT calculations and theoretical investigation of compound 6 and 8 38

32 Synthesis and reactivity of new N-heterocyclic germylene 40

321 Design of rigid new β-diketiminato ligands 40

322 Synthesis of chlorogermylene 14 and new germylene 16 42

323 Reactivity of N-heterocyclic germylene 16 toward NH3 and H2O 45

324 Synthesis of oxo-chloro-germylene 22 and dichlorogermane 23 48

33 Synthesis of the first bis-silylene oxide 28 51

331 Synthesis of the bis-silylene oxide 28 52

332 Chelating coordination of bis-silylene oxide 28 to nickel 55

34 Synthesis of Si2P2-cycloheterobutadiene 31 57

341 Synthesis of N-heterocyclic phosphino silylene 30 59


35 Isolation of an aminosilylene-stannylene dichloride 33 65

36 Exploration and property of SiCSi pincer bis-silylene 34 68

361 Synthesis of the first bis-silylene-based SiCSi pincer arene 35 68

362 Formation of SiCSi pincer arene PdII complex 36 71

363 DFT calculation for explanation of reaction mechanism 74

Table of contents

ii

37 Bis(silylenyl)- and bis(germylenyl)-substituted ferrocenes 76

371 Synthesis of bis(silylenyl)- and bis(germylenyl)-ferrocenes 38 and 40 76

372 Formation of CoICp complexes with 38 and 40 80

373 Formation of bis-silylene 38 bridged complex 44 and 45 83

38 Application of Ni Co complexes as precatalysts 85

4 SUMMARY AND CONCLUSION 89

5 EXPERIMENTAL SECTION 98

51 General section 98

52 Analytical methods 99

53 Starting Materials 101

54 Synthesis and characterization of new compounds 102

521 The first germylene anion 3 and the germylene 4 102

522 Alternative preparation of 3 4 and synthesis of compound 5 103

523 The asymmetric bis-germylene 6 104

524 The first germylene-stannylene 8 105

525 The novel β-diketiminato-type ligand 12 107

526 The new chlorogermylene 14 108

527 The new germylene 16 109

528 Aminogermylene 17 110

529 Germylene hydroxide 18 111


5211 Oxo-chlorogermylene 22 113

5212 β-Diketiminato germanium dichloride 23 114

5213 Amidinato disiloxane 27 115

5214 Bis-silylene oxide 28 116

5215 Bis-silylene oxide nickel complex 29 117

5216 Bis(trimethylsilyl)phosphino silylene 30 118

5217 24-Disila-13-diphosphacyclobutadiene 31 119

5218 Aminosilylene-stannylene dichloride 33 120

5219 46-Di-tert-butylresorcinyl bis-silylene 35 120

5220 SiCSi palladium complex 36 121

5221 Bis(silylenyl)-ferrocene 38 123

5222 Bis(germylenyl)-ferrocene 40 124

5223 Bis(silylenyl)-ferrocene CoICp complex 41 125

5224 Bis(germylenyl)-ferrocene CoICp complex 42 126

5225 Bis(silylenyl)-ferrocene carbonyl CoICp complex 44 127

5226 Bis(silylenyl)-ferrocene Fe(CO)4 complex 45 128

Table of contents

iii

6 REFERENCES 129

7 APPENDIX 138

71 Abbreviations 138

72 Index of compounds discussed in this dissertation 139

73 Crystal Data and Refinement Details 142

74 Publications in this dissertation 156

75 Curriculum Vitae 157

Introduction

- 1 -

1 INTRODUCTION

11 The significance of low-valent group 14 compounds

Generally main-group elements higher than of the third period are classified as

ldquoheavy main-group elementsrdquo some of which show abnormal physical and chemical

properties For example Br(VII) is a stronger oxidant than Cl(VII) This different

behavior of high-valent main-group elements can be attributed to the relativistic

effect[1]

of electrons The contraction of all s-orbitals triggered by the relativistic effect

leads to a greater energy difference between s- and p-orbitals in higher period

elements which increases the difficulty of a sp-hybridation Moreover the energy

difference between s- and p-orbitals for elements in the d-district of the fourth period

and f-district of the sixth period vary unconventionally resulting in the so called

ldquosecondary periodicityrdquo of forth and sixth period elements Therefore ns2 electrons in

the valence shell of heavy main-group elements play an essential role for their

chemical properties[2]

During the organometallic research of main group elements a

series of novel compounds have been discovered and new synthetic methods as well

as theoretical insights in their chemistry have been developed and summarized[3]

In whole periodic table the difference of property in the group 14 elements (tetrels)

is maximal[4]

In comparison to carbon compounds of Si Ge Sn and Pb are very

different referring to the physical properties chemical behavior and structural features

The theory for carbon chemistry cannot be fit for the chemistry of heavy group 14

elements A typical example is the synthesis of compounds with a silicon-oxygen

double bond (Si=O silanone) Beginning last century the english chemist Frederic

Stanley Kipping manufactured many silicon-carbon compounds and discovered

thereby resin-like products which he called ldquosilicone of ketonesrdquo Kipping coined the

word ldquosiliconerdquo in 1901 to describe polydiphenylsiloxane by analogy of its formula

(Ph2SiO) with the formula of the ketone benzophenone (Ph2CO) Kipping was well

Introduction

- 2 -

aware that polydiphenylsiloxane is polymeric whereas benzophenone is monomeric

and noted that ldquosiliconerdquo and Ph2CO had very different chemistry[5]

The german chemist Richard Muumlller and the american chemist Eugene G Rochow

found almost at the same time a possibility for the industrial production of

dimethyldichlorosilane (Me2SiCl2) the most important precursor for the production of

the silicone in the 1940s[6]

The procedure today is called Muumlller Rochow synthesis

(Scheme 11) From that many researchers synthesized various silicone products but

crystallographically characterized complexes with a donor-stabilized Si=O double

bond were published at the beginning of this century by our group These are the

silanoic ester I1[7]

the carbene-coordinated silanone I2[8]

and the ketone-coordinated

silanone I3[9]

(Scheme 12) The Si=O double bond distance (1532 pm) in I3 is shorter

than the ones in I1 (1579 pm) and I2 (1541 pm) and represents the shortest Si-O

distance in all molecular Si=O compounds hitherto reported[10]

Scheme 11 Muumlller Rochow silicone synthesis

Scheme 12 Isolable donor-stabilized silanoic ester I1 and silanone I2 and I3

The hundred-year story of silicones to monomeric species bearing Si=O double

bonds shows that the silicon atom prefers σ-bonds over double bond (σ- and π-bonds)

That means the classical π-bond is not of first choice for heavy main-group

elements[11]

In other words not only E=X (E = heavy main-group elements X = C N

O) but also E=Ersquo (Ersquo = heavy main-group elements) systems are difficult to stabilize

Introduction

- 3 -

because they easily form σ-bonded corresponding polymers Consequently it is very

challenging to study compounds of heavy main group elements in their low oxidation

state Especially the study of divalent Si Ge and Sn compounds with lone pair

electrons (metallylenes) is one of the most attractive research fields in contemporary

organometallic chemistry[3 12]

In the past thirty years numerous thermally stable unsaturated Si Ge Sn

compounds were isolated which show extremely impressive chemistry[12d 13]

The

difference between C-C and Si-Si double bond is now well-understood[3a]

Very

different reaction mechanisms for the formation of such doubly-bonded carbon and

silicon compounds were throughly discussed The classical C-C double bond can

readily be explained by the valence bond theory and hybridization[14]

The bonding

state in those heavier alkene analogues can be explained by two sets of ns2rarrp

0 donor-

acceptor interactions between two metallylene monomers (Scheme 1 3)[3 15]

Similarly heavier alkyne analogues of main-group elements present also two dative

bonds of ns2rarrp

0 donor-acceptor interactions plus a normal σ-bond between two pz

orbitals[3 12d]

(Scheme 13) But the sp-hybridization for heavy main-group elements

is not realized in their low-valent compounds because sp-hybridization does not lead

to strengthing of terminal σ-bonds to the ligands R

Scheme 13 Nonclassical multiple bond features (E = heavy main-group elements)

Introduction

- 4 -

Until the end of the last century the synthesis of heavier alkyne analogues was an

unsolved problem because of the lack of suitable large substituent At the first the

isolation of a diplumbylene I4[16]

ArrsquoPb-PbArrsquo (Arrsquo = 26-(Tip)2C6H3 Tip = 246-

iPr3C6H2) was reported by Power in 2000 (Scheme 14) As is evident from the

structural parameters of ArPb-PbAr the triple bond character has vanished completely

The Pb-Pb distance (319 pm) in ArPb-PbAr is longer even than that of a normal Pb-

Pb single bond (308 pm) and the CAr-Pb bond vectors are perpendicular to the Pb-Pb

axes (943deg) These two facts illustrated a complete lack of hybridization of lead

atoms and almost exclusive use of p-orbitals in σ-bonds[17]

In 2002 Power reported

the distannyne ArSnequivSnAr I5[18]

(Ar = 26-Dip2C6H3 Dip = 26-iPr2C6H3) containing

a SnequivSn bond length of 2668 pm shorter compared to Sn-Sn single bonds[19]

and

with multiple bond character A trans bent configuration was also observed in I5 but

the Sn-Sn-C angle with 1252deg is far from a perpendicular situation as in I4 In the

same year Power described the first digermyne I6[20]

ArGeequivGeAr In this case the

Ge-Ge bond length of 2285 pm was found to be considerably shorter than normal Ge-

Ge single[13f]

(244 pm) and Ge-Ge double bonds (221-246 pm) indicated multiple

bonding character[21]

The trans-bending angle of Ge-Ge-C (1288deg) in digermyne I6

is slightly larger than that in distannyne I5

Scheme 14 The first isolated formal alkyne analogues of group 14

Introduction

- 5 -

With the appearance of the first structurally characterized disilyne I7[22]

reported by

Sekiguchi the series of heavier alkyne congeners was completed in 2004 The SiequivSi

bond length with 2062 pm was considerably shorter than that of typical Si-Si single

bonds (235 pm) and somewhat shorter than that of typical Si-Si double bonds[13b]

(216 pm) The molecular structure of compound I7 with a Si-Si-Silyl angle of 1374deg

reveals a heavily trans-bent configuration indicating the presence of a nonclassical

triple bond The theoretical calculation approved the trans bent structure and a bond

order of three

12 Heavier carbene analogues of group 14 elements

Isolable carbenes and heavier carbene analogues (metallylenes silylenes R2Si

germylenes R2Ge stannylenes R2Sn plumbylenes R2Pb) can be defined as

stabilized divalent monomers of group 14 elements which can impossibly dimerize or

polymerize continuously due to the thermodynamic andor kinetic stabilization As

already mentioned above in contrast to carbon heavier group 14 elements have a low

tendency of sp-hybridization[11]

Accordingly consists of ns2 valence electrons as a

lone pair and use usually three p-valence-orbitals for the formation of their divalent

species[12c]

The ground state of R2E (E = Si Ge Sn Pb) is thereby a singlet while

the ground state of R2C is a triplet (Scheme 15) because two nonbonding electrons

locate in sp-hybrid orbitals[23]

In order to obtain at ambient temperature isolable metallylenes there are today two

particularly effective stabilization methods First of all these unsaturated compounds

can be thermodynamically stabilized by donor electron delocalization to empty p-

orbital as in the case of silylene I8[24]

and silyliumylidene cation I9[25]

(Scheme 16)

In addition the coordination of ns2 electrons to the empty p-orbital of the neighbor

molecule can be kinetically prevented by bulky substituents which was shown by the

Introduction

- 6 -

successful synthesis of the dialkyl silylene I10[26]

that is stabilized only by the steric

hindrance of four large silyl groups and C-SirarrSi hyperconjugation

Scheme 15 Ground states of triplet-carbene and singlet-metallylenes

Scheme 16 Stabilization of silylenes by π-electron delocalization andor steric

hindrance I8 I9 and hyperconjugation I10

The synthesis of heavier carbene analogues depends on suitable starting materials

with oxidation state II Practically in the case of tin and lead the dihalides SnCl2 and

PdCl2 are stable and suitable as starting materials for isolable SnII and Pb

II

organometallic compounds Many germylenes were synthesized employing the known

germanium dichloride complex GeCl2middotdioxane which is easily available[27]

The

carbene-stabilized SiIICl2

[28] (NHCrarrSiCl2 NHC = (HC-NDip)2C

[29]) was reported

recently by Roesky However it is not a trouble-free starting material for silicon(II)

chemistry due to the difficult removing of by-products derivated by the bulky carbene

(NHC) Otherwise divalent compounds of GeII Sn

II and Pb

II are more stable than the

corresponding SiII analogues Therefore the metallylene synthetic chemistry faces the

main difficulty in the synthesis and isolation of functionalized silylene derivates

Accustomed synthetic approaches of N-heteroleptic silylenes was summarized in

Scheme 17 Their feasibility was also proved by the preparation of new silylenes in

this work

Introduction

- 7 -

Scheme 17 Synthetic approaches of N-heteroleptic silylenes

Usually N-heteroleptic silylenes are accessible from SiIV

-precursors to form SiII-

species using reductants such as Na K or their alloy KC8 lithium or magnesium

naphthalenide etc A usually silylenes[24 26 30]

like I13 with a five- or six-membered

ring system and some three-coordinated silylenes[31]

like I14 are accessible through

the reductive dehalogenation reactions presented in case A Suitable five-coordinated

SiIV

sources I15 could be treated with a non oxygenated strong base resulting in the

corresponding three-coordinated silylenes[32]

I16 The two-coordinated silylene I13

prepared through an acid-base reaction from its four-coordinated precursor was not

observed so far In case C silylenes I18 could be isolated by salt metathesis reaction

during that the halogen atom was substituted by a desired Rsub[33]

With these new

synthetic methods the generation of many imaginable SiII molecules is possible today

Especially more complicated metallylenes for example interconnected or spacer-

separated bis-metallylenes (see next page) can be obtained in good yield Thus more

reactivity will be found in their subsequent reactions

Introduction

- 8 -

13 Bis-metallylenes and metallylenes with several EII cores

The discussion of diplumbylene I4 indicates the strong tendency to transformate a

bis-metallylene instead of triple bond form in the case of lead Scheme 18 shows the

resonance structures of triply bonded I19 and bis-metallylene I20 together with the

donor ligand coordinated interconnected bis-metallylene structure I21 Hitherto the

chemical research in this area made clear that silicon and germanium prefer the type

of structure I19 while the species of lead is more favorable in the state I20[12d]

Corresponding tin species have vacillant structural feature between I19 and I20

depending on the steric demand of R and the packing force in crystals[34]

The donor

ligand coordination with all heavier alkyne analogues leads to the donor-stabilized

bis-metallylene form I21 which possesses an E-E single σ-bond and two ns2 lone

pairs one at each of the E centers[35]

Scheme 18 Resonance structures of nonclassical triple bond and bis-metallylene

According to the bonding state all known bis-metallylenes can be discriminated in

two different types i) ldquointerconnected bis-metallylenesrdquo in which two E atoms are

directly connected by a chemical bond and ii) ldquospacer-separated bis-metallylenesrdquo in

which two EII atoms are separated by bridged atoms or by a broad spacer without an

E-E bond in the molecules[33a 36]

The isolation of bis-metallylenes of heavier group

14 elements has been a major synthetic challenge owing to their tendency to

polymerize Herein a review of this kind of compounds which appeared almost

suddenly just in the last two decades is given

Introduction

- 9 -

Interconnected bis-metallylenes

Interconnected bis-silylenes are shown in Scheme 19 Interconnected bis-silylene

examples were firstly reported by Robinson in 2008[35]

which are a carbene-stabilized

bis-silylene I22 with a SiI-Si

I bond (2393 pm) and a carbene-stabilized bis-silylene

I23 with a Si0=Si

0 double bond (2229 pm) One year later the Roesky group prepared

an interconnected bis-silylene I24[37]

stabilized by amidinato ligands with a SiI-Si

I

single bond (2413 pm) Compound I24 exhibits a gauche-bent geometry Another

amidinato donor-stabilized bis-silylene I25[38]

which was synthesized in last year by

Jones et al possesses trans-bent structure not the gauche-bent form The SiI-Si

I

distance (2489 pm) in I25 is longer than those in I22 and I24 because of the more

sterically hindered amidinato ligands In the same year the synthesis of the first

phosphine-stabilized bis-silylene I26[39]

could be achieved and fully characterized In

this molecule the Si-Si bond with the bond length of 2331 pm is visibly shorter than

those in related molecules Baceiredo et al described that the Si-Si fragment in I26

presents a certain multiple-bond character

Scheme 19 Interconnected bis-silylenes

Interconnected bis-germylenes are shown in Scheme 110 In 2006 Jones and

coworkers reported the first successful isolation of two stable bis-germylenes I27 and

Introduction

- 10 -

I28[40]

which are stabilized by an amidinate and a guanidinate ligand respectively

Their Ge-Ge distances (2672 and 2638 pm) show normal single bond character Two

years later Roesky prepared the bis-germylenes I29[41]

which exhibits a gauche-bent

geometry Since I29 is stabilized by a less bulky amidinate ligands the Ge-Ge bond

with the length of 2569 pm is shorter than those of examples before A different β-

diketiminato ligand stabilized bis-germylene I30[42]

was presented by the work group

of Leung in which the Ge-Ge bond length (2602 pm) is somewhere in between The

reduction of NHCrarrGeCl2 (NHC see Scheme 110) employing magnesium(I)

reagents[43]

furnished the carbene-stabilized bis-germylene I31[44]

with a Ge0=Ge

0

double bond (2349 pm) which is the homologous compound of I23 Theoretical

analyses of I31 suggest a singlet germanium(0) dimer (Ge=Ge) datively coordinated

by two NHC ligands In the last year Jones again reported a bis-germylene I32[38]

which is structurally comparable with I27 and I28 But the Ge-Ge distance in I32 is

similar with that of I30

Scheme 110 Interconnected bis-germylenes

Interconnected bis-stannylenes are shown in Scheme 111 Very interestingly the

introduction of SiMe3 instead of H at the para-position of the aryl ring in distannyne

I5 induced the first bis-stannylene I33[34]

without alteration of the steric crowding

near the tin center The small Sn-Sn-C angle (993deg) and the long Sn-Sn distance

(3066 pm) in I33 indicate two stannylene moieties connected with a single bond and

Introduction

- 11 -

without the sp-hybridization In the similar work of Power et al in 2010 the

introduction of GeMe3 substituents of aryl rings at the para-position resulted also in

single bonded bis-stannylene I34[45]

with Sn-Sn distances of 3077 pm and ldquosharprdquo

Sn-Sn-C bending angles of 978deg With the bis-stannylene I35[46]

Jambor showed that

without the use of bulky substituents such as 26-disubstituted aryl groups a bis-

stannylene can be stabilized by intramolecular NrarrSn interactions The less bulky

aryls (aryl = 26-(Me2NCH2)2C6H3) in I35 led to the shorter Sn-Sn single bond (2971

pm) and a trans-bent angle of 943deg as in the diplumbylene I4 The first amidinato

coordinated bis-stannylene I36[38]

with a Sn-Sn single bond was reported by Jones et

al last year Its structural features are highly similar to the germanium homologue

compound I32

Scheme 111 Interconnected bis-stannylenes

Spacer-separated bis-metallylenes and species containing several EII cores

Lappert and Veith reported on the isolation of divalent germanium and tin

compounds very early[47]

Many of these from the 1970s and 1980s that were

described without X-ray characterization will not be discussed here The spacer-

separated bis-germylene I37[48]

and bis-stannylene I38[48]

(Scheme 112) appeared

first of all of this compound class in 1988 The work group of Veith introduced a facile

Introduction

- 12 -

synthetic method by which tetralithium amide reacted with two equivalents of

GeCl2middotdioxane or SnCl2 to give the corresponding products in over 60 yield In 1990

two interesting germylenes I39[49]

and I41[50]

were reported by Lappert and Power In

comparison to the isolable isonitrile (R-N+equivC

minus) until now it was not possible to

stabilize its homologous derivates of the heavier group 14 elements Compounds I39

and I41 can be considered as the dimer (I39) and trimer (I41) formed after

oligomerization of the unstable germaisonitrile analogue (R-N+equivGe

minus) Nevertheless

compounds with two germylene moieties at the time could be seen as impressive

achievements in the divalent germanium chemistry Another dimer of germaisonitrile

bis-germylene I40[51]

was reported by Roesky in 1997 After this the first stable

dimeric silaisonitrile I42[52]

generated through the reduction of carbene stabilized

dichlorosilaimine (NHCrarrSi(Cl2)=NAr Ar = 26-Dip2-C6H3) with KC8 was presented

by the work group of Roesky in 2011 The lengthy synthetic protocol bulky protecting

groups and a low yield (21) of I42 indicate a more difficult synthetic chemistry

necessary for the synthesis of the latter silicon compound However a trimer (tris-

silylene) of silaisonitrile (R-NequivSi) the silicon analogue of I41 is now just a dream of

synthetic chemists

In 1991 two bis-stannylenes (micro-chlorotin(II) amides (micro-Cl-Sn-NR2)2) I43 (NR2 =

N(CMe2)2(CH2)3) and I44 (R = SiMe3) in which two stannylene moieties are bridged

by two chlorine atoms were synthesized by Lappert et al[53]

Surprisingly X-ray

analyses of the two crystals show that I43 is the cis-isomer but I44 has the trans-

configuration In contrast a new bis-stannylene (ClSn-micro-N(Naph)SiMe3)2 I45[54]

was

characterized with two bridged nitrogen atoms by the same work group The Sn-N

bonds of 2438 pm in I45 are much longer than the terminal Sn-N bonds of 2069 pm

in I44 The Sn-N-Sn-N ring in I45 is slightly puckered and bears trans-Cl atoms

Instead of halogen atoms in bis-germylene I46[55]

two terminal N atoms of the azide

groups bridge two germylene parts forming a planar four-membered Ge2N2 ring

Otherwise the germylene centers of I46 are tetracoordinated due to two additional

OrarrGe dative bonds The N-bridged three-core germylenes I47 and stannylenes I48

Introduction

- 13 -

were prepared by Veith in 1991[56]

For four of six molecules X-ray crystal structure

determinations have been carried out which reveal the molecules to be built of a

diamond-lattice-like skeleton The top N atom coordinates to all three germylene

(stannylene) parts and another N atoms bridge with the neighboring two germylene

(stannylene) parts The chair-form six-membered E3N3 ring contains three N-H bonds

and traps one halogen atom (Cl Br I) with the three hydrogen atoms

Scheme 112 Spacer-separated metallylenes I37-I48

The by 14-diamine molecules separated bis-stannylenes I50 and I51 were prepared

from the chlorostannylene dimer I44 and the corresponding dilithium diamide by

Lappert and co-workers in 1994 (Scheme 113)[57]

Bis-germylene I49 was similarly

prepared by the reaction of the GeII homologous derivate ClGeN(SiMe3)2 of I44 with

dilithium diaminobenzene and marked a new development at that time In 1997

Lappert et al reported a new 13-diamine bridged bis-stannylene I52 and a stannylene

I53 with the three SnII cores employing dilithium meta-diamide

[58] The synthesis of

I52 is similar to I50 while I53 was isolated by treatment of the substituted

Introduction

- 14 -

diaminobenzene with Sn(N(SiMe3)2)2 in a ratio of 23 Evidently the formation of I53

involves unexpected C-H activations of the 2-position of 13-diaminobenzene and

eliminations of amine HN(SiMe3)2 The 32 reaction of Sn(NMe2)2 with sterically

bulky aromatic amines (DipNH2 or MesNH2) in toluene can be controlled giving the

heteroleptic stannylenes I54 and I55[59]

in which sterically less bulky NMe2 groups

serve as bridges and one SnII center between two bulky R groups remains its two-

coordination The isolation of the first GeII and Sn

II amide dimers I56 and I57

bridged by the NH2 groups was presented in 2005[60]

They were synthesized by the

reaction of bulky low-valent organo GeII and Sn

II halides (ArE

IICl E = Ge Sn Ar see

Scheme 113) with dry ammonia The Ge2N2 or Sn2N2 cores in I56 and I57 are planar

with rhombohedral shapes and with acute angles near 80deg at Ge or Sn and wider

angles near 100deg at N

Wright 1997

I54 R = Mes I55 R = Dip

I52 Lappert 1997

SnNMe2

Sn

Me2N

NR

NR

NN

SiMe3

E

(Me3Si)2N

E

Me3Si

N(SiMe3)2

N

N

SiMe3

Sn

(Me3Si)2N

Sn

Me3Si

N(SiMe3)2

Lappert 1994

I49 E = Ge I50 E = Sn I51 Lappert 1994

NN

N N

SnSn

SiMe3

SiMe3

Me3Si

Me3Si

I53 Lappert 1997

NN

N N

SnSn

SiMe3

SiMe3

Me3Si

Me3Si

Sn

Sn

Power 2005

I56 E = Ge R = Dip

I57 E = Sn R = Tip

R

RE

NH2

E

H2N

R

R


The discovery of the first spacer-separated bis-silylene I58 (Scheme 114) was

made by Lappert et al in 2005[61]

It was synthesized by reductive dehalogenation of

the bis-dichlorosilane precursor with KC8 With the bis-functionality of I58

eventually a macrocycle metal-complex could be formed but the rigid backbone does

not allow a chelating coordination to a single core In addition Power tried oxidative

Introduction

- 15 -

addition reactions of his Sn and Ge alkyne analogues (I5 and I6 Scheme 114) with

trimethyl silyl azide (Me3SiN3) and adamantanyl azide (Ada-N3) giving the spacer (N-

SiMe3 or N-Ada) separated bis-stannylenes I59[62]

and bis-germylene I60[63]

and with

azobenzene (PhN=NPh) giving the spacer (PhNNPh) separated bis-germylene I61[62]


respectively The similar reaction of bis-germylene I29

with azobenzene furnished also the addition product the spacer bridged bis-

germylene I63[64]

with simultaneous cleavage of the Ge-Ge single bond as observed

by Roesky in 2010 At the same time So et al activated the Si-Si single bond of bis-

silylene I24 with phenyl acetylene resulting in the ethylene bridged bis-silylene I64[65]

Many spacer separated bis-germylenes and bis-stannylenes[66]

(I65-I74) were

successfully designed and isolated by Hahn et al for the use as promising chelating

ligands in coordination reactions A few transition-metal complexes of them were

prepared by his research group too (see p 18)


In 2011 after the synthesis of the first oxygen bridged bis-silylene[32a]

(aLSi-O-Si

aL

aL = PhC(

tBuN)2

minus) in the course of this PhD work other four analogous were reported

Introduction

- 16 -

which are oxygen bridged bis-germylenes I75[67]

I77[68]

bis-stannylene I78[68]

and

sulfur bridged bis-germylene I76[67]

(Scheme 115) Bis-germylene oxide I75 and

sulfide I76 were synthesized in the work group of So et al by the dehalogenation of

LGeCl (L = amidinate in I75) with KC8 and then the oxidation with trimethylamine

N-oxide (Me3NO) or with elemental sulfur Otherwise Powerrsquos new compounds I77

and I78 were accessible by oxidative addition of alkyne analogues I5 and I6 using the

stoichiometric oxygen transfer reagent pyridine N-oxide (C5H5NO) In the last two

decades several cubanes of attractive tetra-metallylenes with GeII Sn

II Pb

II like I79

were presented[69]

(Scheme 116) Because they are somewhat far from discussed

metallylenes in structural features and synthetic approaches they are not discussed

and shown in detail here The synthesis of the still unknown SiII analogue I80 a

tetramer of silaisonitrile (R-NequivSi) remains as a fascinating challenge

Scheme 115 New bis-metallylenes bridged by a single atom

Scheme 116 Cubane-like tetra-metallylenes of heavier group 14 elements

14 Coordination chemistry of chelating metallylene ligands

The interaction between the central atom and the donor in transition-metal

complexes depends on their electron configuration There are two- and three-

coordinated metallylenes in which the empty np-orbitals are stabilized by

Introduction

- 17 -

intramolecular electron delocalization or by the third donor-ligand donation

respectively Therefore if two types of metallylenes serve as donor-ligands for

transition-metals the interaction of these p-orbitals with the corresponding metal d-

orbitals is essentially different For example two silylenerarrM complexes are shown

in Scheme 117 Complex I81 shows clearly σ-donorπ-acceptor interaction[70]

while

the Fe atom in complex I82[71]

contains only a σ-donor bond from the silylene subunit

In this sense three-coordinate metallylenes as σ-donor ligands are more similar to

isoelectronic triorganophosphine ligands[33a b]

in I83 (Scheme 117) In Table 11 the

difference of three-coordinate silylenes and triorganophosphines are compared and

shown in detail

Scheme 117 The σ-donorπ-acceptor or only σ-donor coordination

Table 11 Comparison of three-coordinate silylenes and phosphines

three-Coordinate silylenes Phosphines (PR3)[72]

Synthesis difficult synthetic approaches well-established synthetic procedures

Embellishment only few scaffolds are known numerous structural transformations

and various substituents of R

Stability air and moisture sensitive normally stable in air

Property easily oxidative addition

much stronger σ-donor ligand

multivariate chemical behavior

seldom oxidative addition

strong σ-donor ligand

predictable chemical behavior

Complex only few transition-metal complexes complexes with numerous metals

State of

Development

underdeveloped chemistry fully established

Introduction

- 18 -

In coordination chemistry the spacer separated bis-metallylenes are at the same

time bidentate chelating ligands despite almost all of them were not or could not be

used as chelating ligands Until 2008 only a few chelated transition-metal complexes

coordinated by isolable spacer separated bis-metallylenes were reported They are the

bis-germylene I65 coordinated Mo(CO)4 complex I65-Mo[66b]

and bis-stannylenes

I73 I74 coordinated Ni0 complexes

[66c] I73-Ni I74-Ni (Scheme 118) reported by

Hahn et al Another bis-germylene complex I29-Fe[64]

with two Fe cores presented

by Roesky in 2010 does not comprise chelating coordination at all The reason for the

lack of representative bis-metallylenes in coordination chemistry is that not only the

formation and isolation of such complexes are very difficult but also the design and

synthesis of bis-metallylenes themself are sometimes infeasible Additionally the air-

and water-sensitivity of these compounds causes many unexpected side-reactions In

general metallylene transition-metal complexes are still limited in using metallylenes

containing single EII cores (E = Si Ge Sn)

Scheme 118 Known complexes of spacer-separated bis-germylenes and stannylenes

The successful usage of bidentate phosphanes in many catalytic transformations

originates from their convenient electronic properties and the variable steric

protection Among those chelating bis-phosphane I84[73]

(BINAP Scheme 119) with

Introduction

- 19 -

backbone chirality can lead to excellent enantioselectivity compared to monodentate

phosphines With ferrocendiyl bridged ligands I85 bimetallic complexes are easily

prepared[74]

Furthermore bis-phosphane ligands like I86 are superior bridges for

heterodinuclear complexes in catalytic hydrogenation[75]

Pincer arenes consisting of

a central aromatic backbone linked to two phosphane parts by different spacers are

particularly attractive because of their feasible structural tuning with many choices of

donor groups[72 76]

Recently the chemistry of pincer-ligated transition-metal

complexes underwent rapid developments and has been used for several intriguing

chemical transformations[72b 77]

The coordination chemistry of the most common

pincer ligands such as NCN- PCP- and SCS-type ligands toward transition-metals in

I87 (Scheme 119) was explored extensively[72b 77]

Pincer arenes with stronger σ-

donor sites E than those provided by group 15 and 16 atoms are very attractive for the

synthesis of more electron-rich transition-metal complexes for activation of small

molecules On the other hand transition-metal complexes with ligands like I84-I87

containing EII cores (E = Si Ge Sn) were scarce before 2009

Scheme 119 Bidentate phosphanes for transition-metal complexes

The challenge of spacer-separated bis-metallylenes as novel bidentate σ-donor

ligands for transition-metal complexes are intriguing because of their unique structure

and their coordination ability Therefore transition-metal complexes with chelating

Introduction

- 20 -

bis-metallylenes which were not throughly uncovered[66b c 78]

have received more

and more attention To date the new development of bis-metallylene synthesis

enables the isolation of their transition-metal complexes containing EII-based

functional groups as chelating ligands These complexes may provide access to their

potential application in which they can play a key role as intermediates in transition-

metal catalyzed transformations[70c 79]

Motivation

- 21 -

2 MOTIVATION

As pointed out in the introduction the metallylene synthetic chemistry is a fast

developing field with a great potential to find novel metallylenes with new

functionalities which would be the basis for the development of new kinds of

transition-metal complexes I am particularly interested in the synthesis of new types

of compounds containing divalent group 14 elements and to study their coordination

properties towards transition-metals New metallylenes could serve as very strong σ-

donor ligands for the generation of transition-metal complexes with unusual high

electron density at the metal site which could possess unique chemical properties

The three reports of transition-metal complexes[66b c]

containing bidentate bis-

germylene (stannylene) ligands were discussed in the ldquoIntroductionrdquo of this work

This potential of bis-metallylenes used as chelating ligands in coordination chemistry

prompted me to investigate new transition-metal complexes along with the

development of a new low-valent Si Ge and Sn chemistry

In this work three main points will be addressed i) the design and synthesis of new

ligand stabilized heavier carbene analogous (metallylenes) and interconnected bis-

metallylenes containing low-valent Si Ge Sn ii) the exploration of synthetic

approaches towards different spacer separated (bridged) bis-metallylenes iii) the

investigation of the properties and coordination abilities of new metallylenes (bis-

metallylenes) to transition-metals

The β-diketiminato and amidinato scaffolds I and II were chosen for the

stabilization of the reactive divalent group 14 units (Scheme 21) The known

metallylene halogenide compounds[31a 32b 80]

III and IV were used as the direct

precursors for the preparation of novel mono- and bis-metallylene derivates

Motivation

- 22 -

Scheme 21 Synthesis of new metallylene derivates from precursors

Scheme 22 Coordination of new spacer-separated bis-metallylene to transition-metals

Using isolated products as precursors complexes with different electronic

configurations and activities can be obtained and further modified through

coordination to transition-metals and varying substituents as ligands (Scheme 22)

This development may provide new divalent group 14 element-based functional

ligands in coordination chemistry towards transition-metals As spacer units for the

bis-metallylenes should serve 13-functionalized arene ferrocene and chalcogen

elements (O S Se) The promising application of new metallylene-metal complexes

will be investigated as the precatalyst in organic reactions

Results and Discussion

- 23 -

3 RESULTS AND DISCUSSION

31 Synthesis of Ge Sn carbene analogues and their derivates

In this PhD work the abbreviation of nacnacmacr is used only for the Dip-substituted β-

diketiminato ligand[81]

(CH[CMe(NDip)]2macr Dip = 26-iPrC6H3) The synthesis of β-

diketiminato ligand stabilized germanium complexes (nacnac)GeCl 1[80]

and

(nacnac)GeCl3 2[82]

were reported through the reaction of GeCl2sdotdioxane or GeCl4

with the corresponding Li(nacnac) reagent These compounds can be obtained in high

yield after recrystallization and were used as starting materials for new low-valent

germanium derivates

311 Isolation of the first germylene anion salt 3 and germylene amide 4

Treatment of β-diketiminato germylene chloride 1 with excess of elemental

potassium at ambient temperature in THF yielded the first cyclogermylidenide

derivative 3[83]

which was isolated by fractional crystallization from diethylether in

the form of its potassium salt in 33 yield as pale yellow crystals Moreover the

reduction of 1 led also to the β-diketiminato germylene amide 4[83]

(nacnac)Ge-NH-

Dip which was isolated by fractional crystallization from hexane solution as yellow

crystals in 31 yield (Scheme 31) Both 3 and 4 have been characterized by NMR

spectroscopy (1H

13C) EI-mass spectrometry (only for 3) and correct elemental

analyses

Scheme 31 Synthesis of the germylenide potassium salt 3 and germylene amide 4


- 24 -

The 1H-NMR spectrum of compound 3 displays two sets of doublets for the Dip-

methyl groups in the range from 108 to 112 ppm Two additional singlets at 184 and

262 ppm were assigned to methyl groups of the five-membered ring Resonances for

the CH of iso-propyl appears at 298 ppm as septets The resonance of the β-H proton

at the GeNC3 ring appears at δ = 618 ppm One set of resonances for aromatic

protons of Dip-groups appears in the range of 691-698 ppm In addition the

diethylether molecule was observed by 1H-NMR spectroscopy The molar ratio of

ether was determined by integration of the appropriate resonance signals in the 1H-

NMR spectrum of 3 This amounts to 22mol and the determined composition fits

well with the elemental analytical data

Complex 3 is an Et2O coordinated potassium germylene anion salt according to the

1H- and

13C-NMR spectra Its structure has been established by a single-crystal X-ray

diffraction analysis (Figure 31 left) It reveals a dimeric half-sandwich complex

interconnected via intermolecular GerarrK dative bonds In the structure each half-

sandwich moiety consists of a K(OEt2)2 cation η5-coordinated to the anionic five-

membered planar GeNC3 ring The K1-Ge1 distance of 3449(1) pm is shorter than

the intermolecular K1-Ge1rsquo distance of 3573(1) pm It is noteworthy such shorter K-

Ge distances have been observed in a related dipotassium (18-crown-6)

tetraphenylgermol dianion (330 335 pm)[84]

as well as in a (18-crown-6)-solvated

potassium silylgermanides (342 pm) with a tetravalent germanium atom[85]

Accordingly the K-C(ring) distances in 3 (3092(2)-3330(2) pm) are also longer than

those observed in the aforementioned dipotassium germol dianion (288-317 pm) The

Ge1-N1 distance of 1944(2) pm are shorter than those Ge-N distances in 1[80]

but

longer than that corresponding values in a N-heterocyclic 6π aromatic

germyliumylidene cation[86]

(189 pm) and the heterofulvene-like germylene[87]

(186 pm) Additionally the Ge1-C2 distance (1887(2) pm) the endocyclic C-C

distances (C2-C3 1411(3) C3-C4 1371(3) pm) and the C4-N1 bond length (1382(3)

pm) suggest significant π-resonance stabilization within the six-membered GeNC3

ring In line with that the remarkable deshielding of the resonance signal (618 ppm)


- 25 -

for the β-H atom in the 1H-NMR spectrum is in agreement with a considerable hetero-

Cpmacr-like resonance stabilization in the five-membered GeNC3 ring (Figure 31 right)

The latter is also supported by density functional theory (DFT) calculations (see

section 313) Hereafter the lithium complexes of N-heterocyclic germylidenide and

stannylidenide anions[88]

[(THF)Li-η5-EC(tBu)C(H)C(

tBu)N(Dip) E = Ge Sn] were

presented with a similar reductive reaction

Figure 31 Molecular structure of germylene anion salt 3 (left) and hetero-Cpmacr-like

resonance structure (right) Thermal ellipsoids are drawn at 30 probability level

Hydrogen atoms are omitted for clarity Selected bond lengths [pm] and angles [deg]

Ge1-C2 1887(2) Ge1-N1 1944(2) Ge1-K1 34485(6) Ge1-K1rsquo 35728(7)

K1-C2 3092(2) K1-C3 3122(2) K1-C4 3330(2) K1-N1 3402(2) K1-Ge1rsquo

35728(7) N1-C4 1382(3) C1-C2 1516(3) C2-C3 1411(3) C3-C4 1371(3)

C4-C5 1508(3) C2-Ge1-N1 843(1) C4-N1-Ge1 1130(1) C3-C2-C1 1202(2)

C3-C2-Ge1 1116(2) C1-C2-Ge1 1281(2) C4-C3-C2 1174(2) C3-C4-N1

1135(2) C3-C4-C5 1254(2)

The formulation of the resonance structure clarifies that the nitrogen atom has a

higher affinity to carbon instead to germanium (Scheme 32) The mesomer 3c is

energetically less favorable than 3a and 3b This explains also that the Ge1-C2 bond

(1887(2) pm) is shorter than the Ge1-N1 bond (1944(2) pm) in 3


- 26 -

Scheme 32 GeNC3-ring resonance structures of germylenide anion of 3

The 1H-NMR spectrum of compound 4 shows four sets of doublets and one

multiplet for methyls of Dip-groups in the range from 091 to 130 ppm Resonances

for methyl-groups of the six-membered ring appear at δ = 162 ppm as one singlet

Multiplets in the range of 329-340 are assigned to CH-groups of iso-propyl groups

The resonance of CH proton at the GeN2C3 ring appears at δ = 503 ppm One singlet

at δ = 564 ppm is assigned to NH-groups One set of resonances for aromatic protons

of Dip-groups appears in the range of 683-718 ppm

Figure 32 Molecular structure of germylene amide 4 Thermal ellipsoids are drawn

at 30 probability level Hydrogen atoms are omitted for clarity Selected bond

lengths [pm] and angles [deg] Ge1-N1 2051(2) Ge1-N2 2026(2) Ge1-N3

1905(2) N1-C2 1329(3) N2-C4 1332(3) C1-C2 1518(3) C2-C3 1394(3)

C3-C4 1394(3) C4-C5 1512(3) N3-Ge1-N1 9720(8) N3-Ge1-N2 8876(9)

N2-Ge1-N1 8822(8) C2-N1-Ge1 1229(2) C4-N2-Ge1 1240(2) N1-C2-C3

1227(2) C4-C3-C2 1269(3) N2-C4-C3 1239(3)


- 27 -

The structure of compound 4 was established by single crystal X-ray diffraction

analysis (Figure 32) It consists of a slightly puckered six-membered GeN2C3 ring

with geometric parameters similar to the corresponding parameters found in precursor

chlorogermylene 1[80]

The sum of bond angles at Ge atom of 2742deg is comparable to

that of 1 (2815deg) implying the presence of a lone pair of electrons at the Ge center

The Ge-N distances in 4 (2026(2) and 2051(2) ppm) are somewhat longer than those

in chlorogermylene 1 (1988(2) and 1997(3) ppm) In the structure of 4 the terminal

Ge-N distance of 1905(2) pm is significantly shorter than those the endocyclic ones

(2026(2) 2051(2) pm) because it is a common covalent bond and stronger than

dative NrarrGe bonds

A plausible mechanism for the formation of 3 and 4 is proposed as depicted in

Scheme 33 The reduction of (nacnac)GeCl 1 by elemental potassium gives the N-

heterocyclic potassium germylidenide 3d as initial transient species The latter

undergoes a ring contraction to give the transient germylene amide 3e which reacts

with 1 in a salt metathesis reaction affording the Dip-N-bridged bis-germylene 3f

Reductive fission of a Ge-N bond in 3f by elemental potassium leads to the germylene

anion potassium salt 3 and the potassium β-diketiminato-GeII amide (nacnac)Ge-NK-

Dip The formation of 4 from (nacnac)Ge-NK-Dip needs a subsequent protonation

from the solvent in an inert atmosphere

Scheme 33 The mechanism of the formation 3 and 4


- 28 -

312 Reduction of (nacnac)GeCl3 2 with KC8

This part of the research is the cowork with Shenglai Yao (TU Berlin)

Another reduction experiment of the related β-diketimiate-substituted

organogermanium trichloride 2[82]

(nacnac)GeCl3 with KC8 was investigated The

reaction of 2 with KC8 in THF led to a brown-red mixture from which colorless

crystals of the known β-diketiminato potassium complex K(nacnac)[89]

have been

isolated as side products along with deep-red crystals of the remarkable novel cluster

species 5[83]

in low yield (3 Scheme 34) In contrast reaction of 1 with elemental

potassium in toluene even at 0 degC led merely to the complete replacement of Ge by K

via reduction of GeII to elemental Ge

0 powder and concomitant formation of the

aforementioned β-diketiminato potassium complex

Scheme 34 Reduction of (nacnac)GeCl3 2 with KC8

The X-ray crystal diffraction analysis of 5 revealed a dipotassium salt of the first

ldquoheavyrdquo cyclobutadiene-like dianion (CBD2-

) consisting of a Ge4 core (Figure 33)

Remarkably to date only a few metal complexes of ldquoheavyrdquo CBD2-

have been

reported featuring a Si4 and Si2Ge2 core[90]

Compound 5 consists of a planar

Ge4(nacnac)22macr dianion in which the two unusual chelating nacnac-ligands are

attached to the Ge4 core each with terminal Ge-C and Ge-N σ-bonds The dianion is

connected by two η3-coordinated K(OEt2) cations each coordinated to Ge1 Ge2 and

N2 and Ge1rsquo Ge2rsquo and N2rsquo respectively The K-Ge distances of 3355(1) pm (K1-

Ge1) and 3477(1) pm (K1-Ge2) are similar to those K-Ge distances in 3 and in

related potassium germanides[84b 85]

The molecular structure of 5 is also notable for


- 29 -

the parallelogram-like configuration of the planar Ge4 moiety The Ge1-Ge2 of

2512(1) pm and Ge1-Ge2rsquo distance of 2553(1) pm are close to the Ge-Ge single

bonds observed in bulky substituted cyclotetragermanes (ca 251 pm)[91]

and longer

than those in Ge4Co complexes[90d]

(235-237 pm) while the transannular Ge2-Ge2rsquo

distance of 2747(1) pm is much longer Interestingly despite of the pyramidal

coordination environment of the Ge atoms the Ge42macr core of 5 shows extremely

strong aromaticity as supported by DFT calculations (see section 313)

Figure 33 Molecular structure of 5 containing a Ge42minus

cluster Thermal ellipsoids

are drawn at 30 probability level Hydrogen atoms are omitted for clarity

Selected bond lengths [pm] and angles [deg] Ge1-N1rsquo 1932(3) Ge1-Ge2 2512(7)

Ge1-Ge2rsquo 2553(7) Ge2-Ge2rsquo 2747(1) Ge1-K1 3355(12) K1-N2 2814(3)

K1-Ge2 3477(1) N1-C2 1381(4) Ge2-C3rsquo 2019(3) C2-C3 1369(5) C3-C4

1479(5) N2-C4 1296(4) Ge2-Ge1-Ge2rsquo 657(2) Ge1-Ge2-Ge1rsquo 1143(2) Ge1-

Ge2-Ge2rsquo 578(2) Ge1rsquo-Ge2-Ge2rsquo 564(2) N1rsquo-Ge1-Ge2 8716(9) N1rsquo-Ge1-

Ge2rsquo 1026(9) C3rsquo-Ge2-Ge1 886(1) C3rsquo-Ge2-Ge1rsquo 963(1) C2-N1-Ge1rsquo

1239(2) C3-C2-N1 1205(3) C2-C3-C4 1227(3) C2-C3-Ge2rsquo 1184(3) C4-C3-

Ge2rsquo 1184(3) N2-C4-C3 1220(3)

Scheme 35 shows the assumed mechanism of the formation of Ge42minus

cluster 5 The

product after the first reductive step by KC8 is (nacnac)GeCl 1 which was confirmed

by NMR investigation Chlorogermylene 1 could dimerize by sequential reduction to


- 30 -

a bis-germylene 5a Due to the instability of 5a bearing two bulky nacnac ligands a

transformation could be in the ascendant from dimer 5a to stable P4-like Ge4-tetramer

5b Intermediate 5c could be formed after double intramolecular deprotonation and

elimination of ldquofreerdquo (nacnac)H The excessive KC8 could offer two electrons to

molecule orbitals of Ge4-cluster 5c to furnish the isolated product 5 with a Ge42minus

cluster

Scheme 35 Proposed mechanism for the formation of 5

313 DFT calculations and aromaticity of 3 and 5

The structural feature of 3 leads to a discussion of a possible aromatic character of

the GeNC3-ring in comparison to cyclobutadiene anion Aromaticity is also a key


- 31 -

concept in describing homo-elemental four-membered rings such as the square planar

cyclobutadiene-like dianion Therefore nucleus-independent chemical shift (NICS)

values for the five-membered GeNC3-rings and the four-membered Ge4-ring in

compound 3 and 5 were calculated by Prof Christoph van Wuumlllen (University of

Kaiserslautern) Since their introduction NICS[92]

values have been used as an

aromaticity criterion in numerous applications both for organic and inorganic

compounds[93]

NICS values were computed using the molecular structures of compound 3 and 5

from X-ray diffraction analysis The positions of the non-hydrogen atoms were taken

from the X-ray data and kept fixed while the hydrogen positions were optimized

using the TURBOMOLE program package[94]

and its density functional capabilities[95]

an exchange-correlation functional with gradient corrections to exchange and

correlation[96]

(BP86 functional) and polarized triple-zeta (TZVP) basis sets[97]

The

geometry optimizations used density fitting techniques (also known as the RI

approximation)[98]

to evaluate the matrix elements of the electrostatic Coulomb

potential

NICS tensors are defined for any position as the negative magnetic shielding at

that position The magnetic shielding tensors were obtained using the integral-direct

IGLO program[99]

which has been extended to allow the use of density functional

theory[100]

The B3LYP[96a 101]

functional and a basis of IGLO-III[102]

quality were

employed For Ge this is a 4s11p7d1f primitive basis sets in which only the steepest

five s-functions three p-functions and two d-functions are contracted In lack of

IGLO-type basis sets for potassium a TZVDP (triple zeta two sets of polarization

functions) basis was used which will affect the accuracy of the magnetic shieldings at

the centers of the potassium atoms but not elsewhere

The ring centre for each ring system was calculated first from the Cartesian

coordinates and determined the plane through the ring center for which the sum of the


- 32 -

squares of the distance of that plane to the positions of the atoms forming the ring is

minimal This plane was defined as the ring plane A line through the ring center that

is orthogonal to the plane defines the positions of the NICS centers above and

below the ring centers and the local z direction to which the NICS tensors are

transformed to obtain the zz as well as the in plane (mean value of the xx and yy)

tensor components in addition to the isotropic value which is one third of the sum of

the xx yy and zz components The zz component is of particular interest because a

ring current parallel to the ring plane will most strongly be induced if the external

magnetic field is perpendicular to the plane and the magnetic field induced by such a

current will also be in that direction

In addition to the NICS tensor at the ring center (NICS(0) value) its height profile

contains useful additional information[103]

First the height profile discriminates ring

current effects (which are associated with aromaticity) from diatropic contributions

which stem from the proximity of the ring atoms while the latter approach zero

quickly when moving out of the ring plane the former only slowly do so Furthermore

the height profile helps to distinguish π-aromaticity (which is the type of aromaticity

dominant in organic chemistry) from σ-aromaticity (which is found for many

inorganic compounds) if aromaticity only stems from π-electrons which produce no

ring current in the ring plane then the NICS values when moving out of the ring

center first decrease (ie become more negative) before they gradually approach zero

NICS values 100 pm above or below the ring plane (ldquoNICS(1) valuesrdquo)

Table 31 reports NICS results for compound 3 where the region towards to

coordinating K+ ion was denoted as above the plane of the five-membered GeNC3

rings the other side as below Up to 100 pm the results for NICS centers above and

below are quite similar then the results for the positions 150 and 200 pm above the

ring start to be affected by the K+ ion whose distance to the ring plane is 299 pm The

NICS values are negative and the tensors are highly anisotropic the negative isotropic

value stems from the large and negative zz component Furthermore these values fall


- 33 -

off quite slowly when moving out of the ring plane This indicates a diamagnetic ring

current indicative of aromatic behavior Furthermore the most negative values are not

found in the ring center but slightly above which indicates π-aromaticity Of course

this is exactly what has to be expected for a heteroatom analogue of a

cyclopentadienyl anion This is interesting however because the NICS values for

compound 5 see Table 32 show a slightly different behavior again Negative NICS

values fall off slowly but the tensors show a substantial negative in-plane component

up to 200 pm above (or below this is the same in this compound) ring plane This can

be explained by diatropic contributions from the Ge-C and Ge-N bonds which are

nearly perpendicular to the ring plane The second difference between compound 3

and compound 5 is that the NICS values (both the isotropic values and the zz tensor

component) fall off monotonically and have no hump at about 1 pm above the ring

plane The aromaticity of the Ge4 ring in compound 5 must therefore have substantial

σ-character

Table 31 NICS values for compound 3 in ppm (the results are the same for both GeNC3 rings)

isotropic in-plane zz

ring center ndash77 ndash87 ndash56

50 pm above ndash82 ndash50 ndash144

100 pm above ndash73 +16 ndash251

150 pm abovea)

ndash59 +64 ndash298

200 pm abovea)


50 pm below ndash82 ndash46 ndash154

100 pm below ndash74 +04 ndash230



a)

Value affected by a close K+ ion coordinated by the GeNC3 ring


- 34 -

Table 32 NICS values for compound 5 in ppm (the results are the same at both sides of the Ge4

ring)







314 Synthesis of asymmetric substituted bis-germylene 6

As a nucleophile the germanium(II) anion in 3 seems a promising precursor for the

synthesis of asymmetric substituted bis-germylenes and of related heterodinuclear bis-

metallylenes Accordingly the coupling reaction of the nucleophilic GeII centre in 3

with the electrophilic GeII site in 1

[80] was examined and the reaction in THF at -30 degC

yielded a dark red solution from which the bis-germylene 6[104]

has been isolated as

air- and moisture-sensitive dark red crystals in 66 yield (Scheme 36) The isolated

bis-germylene 6 was fully characterized including X-ray diffraction analysis

Scheme 36 Synthesis of bis-germylene 6

The 1H-NMR spectrum of 6 exhibits four sets of doublets in the range from 107

to 124 ppm with the ratio of 121266 which can be assigned to CH3-groups of all

Dip-groups The three singlets in the range of 161-262 ppm can be assigned to the

CH3 groups at the ligand backbones The resonances for the CH of iso-propyl appear

in the range of δ = 301-367 ppm as three sets of septet The remarkable deshielding


- 35 -

of the resonance signal for the ring CH proton of the five-membered GeNC3 ring (δ =

682 ppm) is indicative a stronger 6π-aromatic resonance stabilization compared with

that in the precursor 3 (δ = 618 ppm) The proton resonance signal for the γ-ring

proton in the six-membered GeN2C3 ring of δ = 518 ppm suggests however the

absence of aromatic resonance stabilization In the UV-vis spectra of 6 an absorption

band is observed at 501 nm showing blue shifted in comparison to the values

observed for related amidinate- and guanidinate- substituted bis-germylenes[40]

(I27

and I28 in Introduction) with GeI-Ge

I bonds

315 Synthesis of the first germylene-stannylene 8

The reactivity of 3 towards chlorostannylene 7[80]

(nacnac)SnCl was examined

also by a coupling reaction If (nacnac)SnCl 7 was used as electrophile for the

reaction with 3 in diethylether at -70 degC this furnished the corresponding product

germylene-stannylene 8[104]

which was isolated in the form of dark red crystals in

34 yield (Scheme 37) The new compound 8 was fully characterized including

NMR spectroscopy (1H

13C

119Sn) and X-ray diffraction analysis

Scheme 37 Synthesis of germylene-stannylene 8

The 1H-NMR spectrum of 8 exhibits six sets of doublets in the range from 085 to

129 ppm with the ratio of 666666 for CH3-groups of all Dip-groups The three

singlets in the range of 165-300 ppm can be assigned to the CH3 groups at the ligand

backbones The resonances for the CH of iso-propyl appear in the range of δ = 305-

378 ppm as three sets of septets


- 36 -

A similar situation was observed in the NMR spectra of 8 for the CH moiety at

ligand backbones The deshielding for the ring CH proton of the five-membered

GeNC3 ring in the 1H-NMR spectrum of 8 (δ = 691 ppm) indicates again a stronger

6π-aromatic resonance stabilization than in 3 (δ = 618 ppm) The chemical shift (δ =

510 ppm) for the γ-ring proton in the six-membered SnN2C3 ring of 8 also shows the

absence of aromatic resonance stabilization The 119

Sn chemical shift of 8 at δ -197

ppm in the 119

Sn-NMR spectrum is comparable to the value observed for the precursor

(nacnac)SnCl 7 (δ -224 ppm)[80]

implying a three-coordinated tin atom in solution In

the UV-vis spectrum of 8 an absorption band is observed at 541 nm The latter is

somewhat red shifted in comparison to the values of bis-germylene 6

316 Molecular structures of bis-germylene 6 and germylene-stannylene 8

The new GeI-Ge

I compound 6 represents the first asymmetric substituted bis-

germylene while germylene-stannylene 8 is the first GeI-Sn

I example Their

molecular structures were established by single-crystal X-ray diffraction analysis

(Figure 34) Both N2C3 backbones of the chelating six-membered MN2C3 ring (M =

Ge Sn) are essentially planar but the germanium and tin atoms are out of the

respective plane The five-membered GeNC3 rings in both compounds however are

almost planar The most important structural features are the Ge-M distances and

trans-bending angles The Ge-Ge distance of 25498(8) pm in 6 is the shortest GeI-Ge

I

distance among the distances values observed in known bis-germylenes[38 40-42]

(257-

267 pm see Introduction p 10) but significantly longer than those in digermenes[13f

105] (Ge=Ge 221-247 pm) and digermynes

[3b 20 106] (GeequivGe 221-231 pm) This

relatively short Ge1-Ge2 distance was explained with asymmetric structural feature of

6 and some ionic charge distribution between five- and six-membered rings (see

section 317 DFT calculation)


- 37 -

Structural features of 6 and 8 are shown in Scheme 38 The torsion angles of the

Ge1-Ge2 bond with Ge1-N1-N2 and Ge2-N3-C31 planes in 6 are 1043deg and 1184deg

respectively (1262deg-1387deg in digermyne[20 106]

) In the structure of 8 the Ge-Sn

distance of 27210(4) pm is longer than that value observed for a Ge=Sn double bond

in a germastannene[107]

and also longer than the Ge-Sn distance in

germylstannanes[105 108]

The torsion angles of the Ge-Sn bond with Sn1-N1-N2 and

Ge1-N3-C31 planes are 939deg and 1006deg respectively (943deg in diplumbylene I4)[16]

Such Ge-M (M = Ge Sn) central bond lengths and trans-bent angles are indicative of

the absence of Ge-M multiple bond character of 6 and 8

Scheme 38 Drawing of torsion angles in 6 and 8

Figure 34 Molecular structures of 6 (left) and 8 (right) Thermal ellipsoids (C1-C5

C30-C34 N1-N3 Ge1 Ge2 and Sn1) are drawn at 30 probability level Hydrogen

atoms are omitted for clarity Selected bond lengths [pm] and angles [deg] for 6 Ge1-

Ge2 2549(1) Ge1-N1 2015(4) Ge1-N2 2038(4) Ge2-N3 1951(4) Ge2-C31

1903(5) N1-Ge1-N2 8867(15) N1-Ge1-Ge2 10430(11) N2-Ge1-Ge2


- 38 -

10149(12) C31-Ge2-N3 8447(19) C31-Ge2-Ge1 11890(15) N3-Ge2-Ge1

9962(12) For 8 Sn1-Ge1 27210(4) Sn1-N1 2233(2) Sn1-N2 2231(2) Ge1-

N3 1964(2) Ge1-C31 1915(3) N2-Sn1-N1 8288(8) N2-Sn1-Ge1 9542(5)

N1-Sn1-Ge1 10368(5) C31-Ge1-N3 8433(12) C31-Ge1-Sn1 11495(9) N3-

Ge1-Sn1 10200(6)

317 DFT calculations and theoretical investigation of compound 6 and 8

In order to clarify the electronic structure and bonding nature in 6 and 8 DFT

calculations were performed by Shigeyoshi Inoue (TU Berlin) The simplified

molecules 6a and 8a [6a M = Ge 8a M = Sn (LanL2DZ for Sn)] (scheme 39) in

which the Dip-groups (26-iPr2C6H3) of 6 and 8 were replaced by phenyl groups were

calculated as model compounds DFT calculations of the model compound of 6a was

performed at the B3LYP6-31(d) level and the model compound 8a was performed at

B3LYP level using 6-31G(d) basis set for Ge N C and H atoms and the LANL2DZ

level for the Sn atom

Scheme 39 Computed model compounds 6a and 8a

The computed geometry is in good agreement with the experimental metric

parameters A NBO analysis of 6a and 8a shows that the HOMOrsquos have a large Ge-M

bond character (Figure 35) and the latter derives largely from overlap of Ge and Sn

p-valence orbitals (6a s 1180 p 8820 8a s 978 p 9022) Apparently the

Ge-M bonds possess s character Likewise the Wiberg bond index exhibits Ge-E bond

orders of 08525 (6a) and 07290 (8a) respectively Similar bonding natures have


- 39 -

been identified and reported previously for related GeI-Ge

I dimers

[38 40-42] In addition

the nature of the HOMOrsquos and LUMOrsquos of the model compounds 6a and 8a

corresponds to that of a diplumbylene[16]

which again underlines that the Ge-M bond

in 6 and 8 represents a pure σ-bond

- 1206

LUMO

- 3911

HOMO

- 1138

LUMO

- 4024

HOMO

E [eV]

6a 8a

- 1206

LUMO

- 3911

HOMO

- 1138

LUMO

- 4024

HOMO

E [eV]

6a 8a

Figure 35 Frontier orbitals of model compound 6a and 8a

Interestingly the HOMOrsquos show clearly the presence of p-orbital interaction within

the six-membered MN2C3 ring and a slight interaction with the Ge centre in the

GeN2C3 ring Accordingly the five-membered GeNC3 ring bears a negative net charge

while the six-membered MN2C3 ring has a positive one [NPA charges in the GeN2C3

ring in 6a Ge +065 N (mean) -069 C (mean) 008 vs GeNC3 ring Ge1 +055 N -

066 C (mean) -015 NPA charges in the SnN2C3 ring in 8a Sn +095 N (mean) -

072 C (mean) 007 vs GeNC3 ring Ge +040 N -066 C (mean) -017] Thus the

latter parameters suggest some ionic character of the Ge-M bonds Moreover the

pronounced electron acceptor character of the GeN2C3 ring is also reflected by the

strongly negative values of NICS for 6a and 8a [6a NICS(0) = -88 NICS(1) = -82

8a NICS(0) = -76 NICS(1) = -74] The latter confirms the presence of a 6π-

aromatic stabilization in 6 and 8 as indicated by the 1H-NMR data (see p 34-36)


- 40 -

32 Synthesis and reactivity of new N-heterocyclic germylene

321 Design of rigid new β-diketiminato ligands

The β-diketiminato ligands can undergo several side-reactions such as 13-

coordination C-N-exchange ring-contraction and deprotonation (Scheme 310) A

more rigid β-diketiminato ligand with a six-membered C6-ring in the backbone was

envisioned to prevent those side-reactions and possibly enhance the stability of the

products[81-83 109]

Scheme 310 Coordination possibilities of the classical β-diketiminato ligand

The syntheses of new β-diketiminato ligands[110]

12 and 20 are shown in Scheme

311 They are easily accessible from the N-cyclohexylidene-26-diisopropyl-

benzenamine 9[111]

in a two-step procedure First the deprotonation of 9 with nBuLi in

diethylether leads to the corresponding lithium amide 10 Salt metathesis reaction of

10 with (Z)-N-(26-diisopropylphenyl)benzimidoyl chloride 11[112]

or (Z)-N-isopropyl

benzimidoyl chloride[112]

19 in diethylether then afforded the novel β-diketiminato

type ligand 12 and 20[110]

in 63 and 60 yield respectively The new compounds

12 and 20 have been analyzed by NMR spectroscopy ESI-mass spectrometry X-ray

diffraction and elemental analyses


- 41 -

Et2O - 78degCnBuLi

Et2O - 78degCN

Dip

9

N

Dip

10

Li

N

Ph Dip

Cl

11

12

N

NH

Ph

Dip

Dip

Et2O - 78degC

N

Ph iPr

Cl

19

20

NH

N

Ph

Dip

iPr

Scheme 311 Synthesis of new β-diketiminato ligands 12 and 20

The 1H-NMR spectrum of compound 12 displays four sets of doublet for methyl of

Dip-groups in the range from 117 to 134 ppm The multiplets by 164 ppm and 217

ppm are assigned to CH2 of the six-membered ring The resonance of NH proton

appears at δ = 187 ppm Resonances for the CH of iso-propyl appear at δ = 335 ppm

as multiplet The 1H-NMR spectrum of 20 shows three sets of doublet for the

isopropyl of Dip-groups in the range from 109 to 132 ppm The peaks of four CH2

groups of the six-membered ring appear at δ = 156 208 and 214 ppm as multiplet

The resonances for the CH of iso-propyl appear by 310 and 323 ppm as septet The

resonance of NH group appears at δ = 1203 ppm as doublet because of the 3J-

coupling with neighbor CH group Resonances for aromatic protons of Dip-groups

and phenyl appear in the range of 696-727 ppm for 12 and 713-753 ppm for 20

respectively

NH group connecting with iso-propyl in 20 is also confirmed by single-crystal X-ray

diffraction analysis (Figure 36 and Scheme 312) In compound 12 the N1-C1 bond

length (1360(2) pm) is longer than the N2-C3 bond length (1305(2) pm) due to the

presence of N1-H bond Contrarily the N1-C1 bond length (1309(2) pm) in

compound 20 is shorter than the N2-C3 bond length (1356(2) pm) because of the

presence of N2-H bond


- 42 -

N1C1

C2

C3 N2

Ph Dip

Dip

N1C1

C2

C3 N2

Ph iPr

Dip

1356

1386

1445

1309

1377

1360

1305

1452

12 20

HH

Scheme 312 Bonding situation of new ligands 12 and 20 bond length in pm

Figure 36 Molecular structure of compounds 12 (left) and 20 (right) Thermal

ellipsoids are drawn at 30 probability level Hydrogen atoms are omitted for

clarity Selected bond lengths [pm] and angles [deg] for 12 N1-C1 13600(17) N1-

C13 14349(18) C1-C2 13769(19) C1-C4 15136(18) N2-C3 13046(16) N2-

C25 14297(17) C2-C3 14515(18) C2-C7 15257(18) N1-C1-C2 12221(12)

C1-C2-C3 12230(12) N2-C3-C2 12212(12) For 20 N1-C1 1309(2) N1-C17

1418(2) C1-C2 1445(2) C1-C4 1522(2) N2-C3 1356(2) N2-C14 1461(2)

C2-C3 1386(2) C2-C7 1524(2) C3-C8 1495(2) N1-C1-C2 12080(15) C1-

C2-C3 12151(15) N2-C3-C2 12288(15)

322 Synthesis of chlorogermylene 14 and new germylene 16

Scheme 313 shows the synthesis of chlorogermylene 14[110]

and germylene 16[110]

Through lithiation of compound 12 with nBuLi the Lithium complex 13 was formed

quantitatively The subsequent reaction of 13 with the dichlorogermylene dioxane

complex[27]

(GeCl2middotC4H8O2) affords the desired chlorogermylene 14 in 82 yield


- 43 -

Furthermore germylene 16 was obtained by dehydrochloration of 14 with 13-di-tert-

butyl-imidazol-2-ylidene 15[113]

as a base in 78 yield The composition and

constitution of 14 and 16 were fully characterized by elemental analysis IR and

multinuclear NMR spectroscopies and X-ray crystallography

Scheme 313 Synthesis of chlorogermylene 14 and germylene 16

In the 1H-NMR spectrum of compound 14 resonances of 8 methyl moieties of Dip-

groups appear in the range from 097 to 155 ppm as multiplets The multiplets in the

range of δ = 128-139 and 203-227 ppm are assigned to CH2 moieties of the six-

membered ring Four sets of septets by 317 327 394 and 417 ppm are assigned to

methine protons of the iso-propyl groups The 1H-NMR spectrum of 16 displays three

sets of doublet for methyl moieties of the Dip-groups in the range from 115 to 135

ppm The peaks of four CH2 groups of the six-membered C6-ring appear at δ = 155

204 and 221 ppm as multiplet Resonances for the methine protons of the iso-propyl

groups appear by 369 and 380 ppm as septets A triplet at δ = 415 ppm is assigned to

the proton connecting with C=C double bond This resonance confirms the

deprotonation of C-CH2 to a C=CH structure on the ligand backbone Resonances for

aromatic protons of Dip-groups and phenyl appear in the range of 680-739 ppm for

145 and 675-725 ppm for 16 respectively

The molecular structures of compounds 14 and 16 are shown in Figure 37 and

Figure 38 In compound 14 the six-membered GeN2C3 ring exhibits a boat-like


- 44 -

conformation The C2N2 moiety of the chelating ligand (N1 N2 C1 C3) is nearly

planar and the Ge and C2 atoms are out-of-plane (Ge 37 pm C2 13 pm) In

compound 16 the GeN2C3 ring is almost planar The Ge-N bond lengths in 14

(1980(2) and 1976(2) pm) are longer than those in 16 (1843(3) and 1861(3) pm)

and the N1-Ge1-N2 bond angle (9123deg) in 14 is smaller than that of compound 16

(9509deg) This is probably owing to the dative nature of the Ge-N bonds and the three-

coordinate Ge(II) atom in 14 The Ge-Cl bond length of 2296(1) pm in 14 is

consistent with the value observed in the N-heterocyclic β-diketiminato

chlorogermylene (nacnac)GeCl[80]

The fused cyclohexyl moiety of 14 is distorted

and the phenyl group is oriented in nearly the same direction as the aryl group on the

N2 atom while the C2 C3 C4 and C7 atoms of the fused C6 ring in 14 are coplanar

with the N2C3 ring (C1 C2 C3 N1 N2) while the C5 and C6 atoms deviate above

the plane of the N2C3 ring This conformation of the cyclohexyl moiety is also

observed in compound 16 It is of note that the buta-13-diene moiety (C1 C2 C3 C4

C32) of compound 16 clearly has alternating C-C distances (C32-C1 1498(4) C1-C2

1359(4) C2-C3 1461(4) and C3-C4 1360(4) pm) which is not the case in known

germylene (nacnac)Ge[87]

published in 2006

Figure 37 Molecular structure of compound 14 Thermal ellipsoids are drawn at

30 probability level Hydrogen atoms are omitted for clarity Selected bond

lengths [pm] and angles [deg] Ge1-N1 19760(16) Ge1-N2 19804(17) Ge1-Cl1

22956(7) N1-C1 1342(3) N1-C14 1458(3) C1-C2 1397(3) C1-C8 1502(3)

N2-C3 1333(3) N2-C26 1463(2) C2-C3 1415(3) C2-C7 1522(3) C3-C4


- 45 -

1509(3) C4-C5 1522(3) N1-Ge1-N2 9123(7) N1-Ge1-Cl1 9560(5) N2-Ge1-

Cl1 9392(5) C1-N1-Ge1 12568(13) N1-C1-C2 12352(17) C1-C2-C3

12503(19) N2-C3-C2 12440(18) C3-N2-Ge1 12515(13)



lengths [pm] and angles [deg] Ge1-N1 1843(3) Ge1-N2 1861(3) N1-C3 1426(4)

N1-C8 1442(4) N2-C1 1408(4) N2-C20 1454(4) C1-C2 1359(4) C2-C3

1461(4) C1-C32 1498(4) C2-C7 1525(4) C3-C4 1360(4) N1-Ge1-N2

9509(11) C3-N1-Ge1 300(2) N1-C3-C2 1176(3) C1-C2-C3 1267(3) C2-C1-

N2 1241(3) C1-N2-Ge1 1259(2)

323 Reactivity of N-heterocyclic germylene 16 toward NH3 and H2O

The unusual donor-acceptor properties of the zwitterionic silylene and germylene

were described in our group in 2006[30 87]

In these molecules the exocyclic methylene

group remains more negative charges due to the aromaticity of the center six-

membered ring This implies the presence of two reactivity positions in the molecule

a strong nucleophilic methylene group and a nucleophilic (ns-orbital) and

electrophilic (np-orbital) at the metallylene site Mesomeric structures of zwitterionic

germylene 16 and donor-acceptor properties are shown in Scheme 314


- 46 -

To probe the donor-acceptor properties of zwitterionic germylene 16 its reactivity

toward ammonia and water was investigated Germylene 16 undergoes controllable

ammonolysis and hydrolysis (Scheme 315) Thus treatment of 16 with ammonia gas

at room temperature in toluene resulted in the formation of the corresponding

aminogermylene 17[110]

in high yield (92) Likewise germylene 16 also readily

reacts with water to produce germylene hydroxide 18[110]

nearly quantitatively (95)

Scheme 314 Mesomeric structures of germylene 16 and donor-acceptor properties

Scheme 315 Syntheses of aminogermylene 17 and germylene hydroxide 18

The 1H- and

13C-NMR spectroscopic data of 17 and 18 are very similar to the

corresponding resonances of chlorogermylene 14 appearing at or near the same

chemical shifts In the 1H-NMR spectrum of 17 the protons of the NH2 group appear

at δ = 154 ppm This chemical shift is close to that of the dimeric aminogermylene

(ArrsquoGeNH2)2 (Arrsquo = 26-Tip2C6H3) (δ = 162 ppm)[60a]

The 1H-NMR spectrum of 18

displays a singlet for the hydroxide proton at = 166 ppm which is close to the

respective value observed for the dimeric germylene hydroxide [(nacnac)GeOH]2 (δ =

154 ppm)[114]

The IR spectrum of 18 clearly shows two N-H stretching modes of the

NH2 group at v = 3430 and 3343 cmndash1

respectively These values are similar to those

observed for related aminogermylenes (ArGeNH2)2 (Ar = 26-Dip2-C6H3) (3380

and 3308 cmndash1

) and (nacnac)GeNH2 (3431 and 3333 cm-1

)[115]

A sharp absorption at v


- 47 -

= 3643 cmndash1

that can be attributed to the O-H stretching frequency was observed in

the IR spectrum of 18 This value resembles that of germylene hydroxide

(nacnac)GeOH (3571 cm-1

)[114]

The structure of 17 and 18 are shown in Figure 39 Both compounds 17 and 18 are

monomeric species The structural features of 17 and 18 are very similar and show

close structural parameters compared with that of chlorogermylene 14 As in 14 the

Ge1 and C2 atoms of 17 and 18 slightly deviate from the N2C2 ring (N1 N2 C1 C3)

plane [17 Ge 46 pm and C2 13 pm 18 Ge 49 pm and C2 13 pm] The Ge-N

(ligand) bond lengths (17 2017(2) and 2021(2) pm 18 20054(17) and 20071(16)

pm) of 17 and 18 are longer than the Ge-N(amide) bond length of 17 (1829(3) pm)

Interestingly the Ge-N distance (1905(2) pm) in (nacnac)Ge-NH-Dip 4[83]

due to the

large Dip-substituent is also 8 ppm longer than that of 17 In each case there is clearly

a difference between the dative bond and covalent bond Compound 18 represents the

first monomeric three-coordinate GeII hydroxide in the solid state (Figure 39) owing

the larger steric congestion around the GeII center in contrast to (nacnac)GeOH

[114]

Figure 39 Molecular structures of compound 17 (left) and 18 (right) Thermal


clarity Selected bond lengths [pm] and angles [deg] For 17 Ge1-N1 2021(2) Ge1-

N2 2017(2) Ge1-N3 1829(3) N1-C1 1349(4) C1-C2 1395(4) N2-C3

1336(4) C2-C3 1417(4) C3-C4 1509(4) N3-Ge1-N2 9503(11) N3-Ge1-N1

9709(13) N2-Ge1-N1 8932(10) C1-N1-Ge1 1253(2) C3-N2-Ge1 1247(2)

For 18 Ge1-O1 18249(18) Ge1-N2 20054(17) Ge1-N1 20071(16) N1-C1


- 48 -

1340(3) C1-C2 1402(3) N2-C3 1331(3) C2-C3 1419(3) C3-C4 1509(3)

O1-Ge1-N2 9387(8) O1-Ge1-N1 9529(8) N2-Ge1-N1 8943(7) C1-N1-Ge1

12597(14) C3-N2-Ge1 12515(14)

324 Synthesis of oxo-chloro-germylene 22 and dichlorogermane 23

In order to understand the coordination behavior of ligand 20 experiments using

germanium precursors GeCl2sdotdioxane and GeCl4 were conducted (Scheme 316) The

reaction of compound 20 with one equivalent of nBuLi resulted directly the lithiated

intermediate 21 The subsequent reaction with GeCl2sdotdioxane in Et2O at -78 degC led to

the unusual oxo-chloro-germylene 22 in 80 yield Dichlorogermane 23 was obtained

by reaction of 21 with GeCl4 in toluene at -78 degC through dehydrochloration with 13-

di-tert-butyl-imidazol-2-ylidene 15 as a base in 57 yield The composition and

constitution of 22 and 23 were elucidated by elemental analysis multinuclear NMR

spectroscopies and X-ray crystallography

Scheme 316 Syntheses of oxo-chloro-germylene 22 and dichlorogermane 23

The 1H-NMR spectrum of compound 22 exhibits 6 sets of doublets for 6 methyls of

iso-propyl Five sets of multiplets in the range of δ = 121-206 ppm are assigned to

the CH2 moieties of the six-membered C6-ring Resonances for the CH of iso-propyl


- 49 -

appear at δ = 284 367 and 396 ppm as septet In the 1H-NMR spectrum of 23 peaks

at δ = 113 122 and 137 ppm are for methyls of iso-propyl as doublets Resonances

of three CH2 groups of the six-membered ring on backbone appear at δ = 146 189

and 206 ppm as multiplets Two sets of septets by 332 and 361 ppm are assigned to

the CH of iso-propyl A triplet at δ = 421 ppm is for the proton of C=CH group on

backbone and indicates a dianionic ligand 20 in compound 23 owing to two times

deprotonation with nBuLi and carbene 15 Resonances for aromatic protons of Dip-

groups and phenyl appear in the range of 688-724 ppm for 22 and 701-726 ppm for

23 respectively

The molecular structures of compounds 22 and 23 are shown in Figure 310

Compound 22 represents an imine N-donor stabilized oxo-chloro-germylene and

adopts a pyramidal geometry with the sum of bond angles of 2737deg at the GeII center

The inserted oxygen atom could come in all probability from dioxane molecule in

GeCl2dioxane The cyclohexyl unit on backbone is distorted and the free N2 moiety

is oriented in inverse direction to the cyclohexyl The Ge1-Cl1 bond length of

23073(6) pm in 22 is compatible with the value (2296(1) pm) observed in

chlorogermylene 14 The Ge1-N1 distance of 20908(15) pm is visibly longer than

those of 14 (1980(2) and 1976(2) pm) because of the net NrarrGe coordination bond

without resonance stabilization The Ge1-O1 bond length is normal Ge-O single bond

with a distance of 18265(12) pm Bond lengths of N1-C1 (1284(2) pm) and N2-C7

(1272(2) pm) present clearly C=N double bond while bond lengths of C1-C6

(1525(2) pm) and N6-C7 (1539(2) pm) present normal C-C single bonds

In compound 23 GeIV

atom is tetrahedral coordinated with two nitrogen and two

chlorine atoms All six angles in the range of 1028-1138deg at the GeIV

center are

nearly alike with the angle in methane (1095deg) and indicate a slightly distorted

tetrahedral GeN2Cl2 configuration GeIV

-Cl bond lengths (21339(7) and 21375(9) pm)

in 23 are much shorter than those of germylenes 14 and 22 (229-231 pm) Distances

of the GeIV

-N bonds (1798(2) and 1788(2) pm) in 23 are much shorter than the


- 50 -

NrarrGe dative bonds in 14 17 and 18 (198-202 pm) and the net NrarrGe dative bond

(20908(15) pm) in 22 But they are only slightly shorter than GeII-N distances

(1843(3) and 1861(1) pm) in germylene 16 and GeII-NH2 bond length (1829(3) pm)

in germylene 17 Bond lengths of C1-C2 (1339(4) pm) and C3-C4 (1326(4) pm) in

23 illuminate clearly C=C double bond and distances of N1-C1 (1430(3) pm) and

N2-C3 (1441(3) pm) correspond to C-N single bond



clarity Selected bond lengths [pm] and angles [deg] For 22 Ge1-Cl1 23073(6)

Ge1-O1 18265(12) Ge1-N1 20908(15) O1-C6 1418(2) N1-C1 1284(2) N2-

C7 1272(2) C1-C6 1525(2) C6-C7 1539(2) Cl1-Ge1-O1 9789(4) Cl1-Ge1-

N1 9422(4) O1-Ge1-N1 8158(6) Ge1-N1-C1 11291(12) N1-C1-C6

11484(16) C1-C6-O1 10975(14) C6-O1-Ge1 11838(10) N2-C7-C6

11778(17) For 23 Ge1-Cl1 21339(7) Ge1-Cl2 21375(9) Ge1-N1 1798(2)

Ge1-N2 1788(2) N1-C1 1430(3) C1-C2 1339(4) C2-C3 1486(4) C3-C4

1326(4) N2-C3 1441(3) N2-Ge1-N1 10554(10) N2-Ge1-Cl1 11208(7) N1-

Ge1-Cl1 11381(8) N2-Ge1-Cl2 11201(8) N1-Ge1-Cl2 11082(8) Cl1-Ge1-Cl2

10276(3) C1-C2-C3 1266(2) C4-C3-N2 1209(2) C2-C4-C3 1208(3)

The formation of compound 22 indicates that ligand 20 has a different reactivity to

the derivative ligand 12 due to the exchange of Dip-group with iso-propyl But the

situation of complex 23 shows a possibility of a dianionic chelating coordination[30 87]


- 51 -

of ligand 20 Coordination chemistry with ligand 20 is currently being investigated for

its suitability to serve as bidentate donor ligand for complexes with low-valent Si Ge

and also transition-metals

33 Synthesis of the first bis-silylene oxide 28

Since the successful isolation of halogen bonded silylene and germylene[31a 32b 80]

chemists faced the challenge weather compounds like LEII-X-E

IIL [E = Si Ge Sn X

= O S Se] in which two metallylene moieties are bridged by a single X-atom can be

stabilized at room temperature Key points of this assignment are the identification of

effective ligands for the stabilization of metallylenes and a feasible synthetic route

There is a special interest to synthesize this kind of compounds due to their chemical

nature and coordination properties

Previous attempts to synthesize a stable bis-silylene oxide 28b from silylene 28a[30]

has been unsuccessful The isolated product originating from the reaction of water

with the silylene 28a was the stable siloxysilylene 28c[10a]

(a mixed-valent disiloxane)

(Scheme 317) Recently Roesky et al proposed the formation of bis-silylene oxide 28

(aLSi-O-Si

aL

aL = PhC(

tBuN)2macr) as a reactive intermediate in the reaction of the bis-

silylene I24[37]

(aLSi-Si

aL) with N2O However 28 could be neither detected nor

chemically trapped[116]

By addition of water to two molar chlorosilylene 26[31a]

in

toluene the expected disiloxane 27 could not be isolated from a complicated reaction

mixture (Scheme 317 )

In the following the isolation of the first oxygen-bridged bis-silylene 28 by a facile

synthetic protocol using 1133-tetrachlorodisiloxane[117]

(HSiCl2)2O as starting

material will be described


- 52 -

Scheme 317 Synthesis of siloxysilylene 28c and hydrolysis of chlorosilylene 26

331 Synthesis of the bis-silylene oxide 28

The reaction of 1133-tetrachlorodisiloxane (HSiCl2)2O with 2 molar equiv of

lithium amidinate 25 in diethylether gave the desired disiloxane 27[32a]

in 53 yield

(Scheme 318) The target bis-silylene oxide 28 was readily available by

dehydrochloration of 27 employing 2 molar equiv of LiN(SiMe3)2 in toluene

Recrystallization in toluene afforded pale yellow crystals of 28[32a]

in 76 yield The

molecular structure of new compounds 27 and 28 was characterized by means of

spectroscopy and X-ray crystallography

Scheme 318 Synthesis of disiloxane 27 and bis-silylene oxide 28

The 1H-NMR spectrum of 27 reveals two singlets one for the

tBu groups at δ =

120 ppm and one corresponding to the Si-H protons at δ = 598 ppm as well as one

set of resonances for the Ph group of the amidinate ligand The 29

Si-NMR spectrum of


- 53 -

27 shows a singlet resonance at δ = -1110 ppm The 1H-NMR spectra of 28 displays a

singlet of tBu at δ = 135 ppm and one set of resonances for Ph group in aromatic

resonance region The 29

Si-NMR signal of 28 (δ = -161 ppm) appears shifted ca 95

ppm downfield from the precursor 27 This shift is comparable to that reported for the

triply coordinated silylene alkoxides (aLSiO

tBu) (δ = -52 ppm) and (

aLSiO

iPr) (δ = -

135 ppm)[31b]

respectively

The molecular structure of disiloxane 27 is shown in Figure 311 The center Si1-

O1-Si2 part of molecule 27 was extensively disordered Therefore the X-ray data were

not suitable for accurate discussion Even though the nearly unbent Si1-O1-Si2 angle

(1680deg) in 27 shows a very similar bonded character with sp-hybridized oxygen

bridge in comparison to another disiloxane compounds[118]

The molecule of bis-silylene oxide 28 (Figure 312 left) contains two triply

coordinated Si atoms and two lone pairs one at each of the Si centers Those are two

silylene moieties The sum of bond angles at Si1 and Si2 are 27769deg and 27534deg

respectively which is consistent with the presence of lone pairs In the molecular

structure of 28 Si-O distances of 1641(2) and 1652(2) pm are comparable to those of

siloxysilylene 28c (16442(3) pm and 16501(2) pm) and thus typical for silicon-

oxygen single bonds of other disiloxanes[118]

Moreover as expected for an disiloxane-

like system the Si1-O-Si2 angle of 28 is slightly bent (15988(15)deg) and larger than

that observed for a C-O-C moiety of ethers

DFT calculations of the compound 28 was performed by Shigeyoshi Inoue (TU

Berlin) at the B3LYP level using 6-31G(d) basis set with the GAUSSIAN-03 program

package[101c 119]

The structure obtained by X-ray analysis was used as the input for

these calculation Optimized structure of 28 is shown in Figure 312 (right) DFT

calculations revealed that the Si1-O-Si2 angle deformation energy is very small The

Si-O-Si bond angle of optimized structure is 180deg However the energy difference

between the experimental geometry and linear arrangement is only 071 kJsdotmolminus1

The


- 54 -

HOMO (-0163 eV) and HOMO-1 (-0178 eV) represent mainly lone pairs at Si atoms

The LUMO (-0020 eV) is located on the phenyl group of the amidinate ligand

(Figure 313)

Figure 311 Molecular structure of 27 Thermal ellipsoids are drawn at 30

probability level Hydrogen atoms are omitted for clarity The center Si1-O1-Si2

part was extensively disordered Selected bond lengths (pm) and angles (deg) Cl1-Si1

20349(16) Cl2-Si2 22017(11) Si2-O1 1581(8) Si2-N3 1798(2) Si2-N4

1968(2) Si1-O1 1562(8) Si1-N2 1750(10) Si1-N1 1994(6) Si1-O1-Si2

1680(6)

Figure 312 Molecular structure of 28 (left) and optimized structure (right)

Thermal ellipsoids are drawn at 30 probability level Hydrogen atoms are omitted

for clarity Selected bond lengths (pm) and angles (deg) Si1-O1 1641(2) Si2-O1

1652(2) Si1-N1 1896(3) Si1-N2 1902(3) Si2-N3 1888(2) Si2-N4 1908(3)

Si1-O1-Si2 15988(15) O1-Si1-N1 10417(12) O1-Si1-N2 10535(11) O1-Si2-

N3 10196(11) O1-Si2-N4 10481(12) N1-Si1-N2 6815(10) N3-Si2-N4

6855(11)


- 55 -

Figure 313 Calculated frontier molecular orbitals of 28

332 Chelating coordination of bis-silylene oxide 28 to nickel

To probe the chelating coordination ability of 28 its reactivity toward Ni(cod)2

(cod = cycloocta-15-diene) was investigated Toluene was added to a mixture of bis-

silylene oxide 28 with one molar equiv of Ni(cod)2 at room temperature to furnish an

intensely red-colored reaction solution Recrystallization of the crude product from a

saturated n-hexane solution at -30 degC afforded dark red crystals of the Ni complex

29[32a]

in 91 yield (Scheme 319) The isolated compound 29 is the first bidentate

bis-silylene transition-metal complex This work initiates a significant progress on the

chelating silylene ligand transition-metal coordination chemistry The constitution and

composition of 29 could be determined by NMR spectroscopy elemental analysis

and ESI mass spectrometry

Scheme 319 Synthesis of bis-silylene oxide nickel complex 29


- 56 -

The 1H-NMR spectrum of 29 exhibits one singlet for the

tBu groups at δ = 130

ppm and one set of resonances at δ = 281 295 and 504 ppm for the COD-ligand and

Ph groups of the amidinate ligands The 29

Si-NMR spectrum of 29 exhibits one

singlet (δ = 328 ppm) which shows a downfield shift relative to that of the ldquofreerdquo

ligand 28 The observed downfield shift for the 29

SiII nuclei in 29 clearly suggests the

presence of a bis-silylene chelated complex

The chelating coordination of bis-silylene oxide 28 to Ni0 is confirmed by X-ray

diffraction analysis The molecular structure of 29 is displayed in Figure 314

Complex 29 containing Ni0 is diamagnetic because of 18 electrons in the valence

shell The two silylene subunits and the two ethylenes of the COD-ligand are

tetrahedral coordinated to the nickel atom with the Si1-Ni1-Si2 angle at 6890(3)deg

The Si-O bond lengths in 29 [17011 (15) and 17081(17) pm] are longer than that in

28 [1641(2) and 1652(2) pm] while the Si1-O-Si2 angle of 29 (9344(8)deg) is

significantly smaller than that in 28 The Ni-Si bond lengths [21908(7) and 21969(7)

pm] are slightly shorter than those in silylene nickel complex 29a [2207(2) and

2216(2) pm][120]

but longer than those found in silylene nickel complex 29b

(21395(8) pm)[121]

Scheme 320 shows clear bonded prospect of three complexes

Moreover the Ni-Si bond lengths of bis-silylene nickel complex 29 are longer than

those in ylide-like silylene-nickel complexes [20369(6) and 20597(10) pm][70a b 122]

The strong σ-donor character of bis-silylene ligand 28 causes a more electron rich Ni

center It indicates a somewhat stronger π-back-donation from the nickel atom to the

chelating COD-ligand Therefore the Ni-C distances (2070-2090 pm) in 29 are

shorter than those in Ni(cod)2 (211-213 pm)[123]

and silylene nickel complex 29b

(2130-2146 pm)[121]

The coordination of bis-silylene oxide 28 with other transition-metals (for example

Ti Cu) is currently investigated together with the reactivity of these complexes on

their use as molecular catalysts


- 57 -

29

[Si][Si]

O

Ni

[Si] [Si]

Ni

CO CO

[Si] [Si]

Ni

N N tButBu

Si

N N DipDip

Si

[Si] = [Si] =

29a 29b

2207 2216

2191 2197689deg

934deg

1084deg 1019deg

1708 1701

2139 2139

Scheme 320 Comparison of bonding state in complexes 29 29a and 29b bond lengths in pm

Figure 314 Molecular structure of 29 (left) Thermal ellipsoids are drawn at 30

probability level Hydrogen atoms are omitted for clarity Selected bond lengths

(pm) and angles (deg) Si1-Ni1 21969(7) Si2-Ni1 21908(7) Si1-O1 17011(15)

Si1-N1 18929(19) Si1-N2 1875(2) Si2-O1 17081(17) Si2-N3 18776(19)

Si2-N4 1893(2) Si1-O1-Si2 9344(8) Si1-Ni1-Si2 6890(3) N1-Si1-N2

6941(9) N3-Si2-N4 6954(8)

34 Synthesis of Si2P2-cycloheterobutadiene 31

This part of the research is the cowork with Shigeyoshi Inoue (TU Berlin)

Due to the unique reactivity and electronic properties compounds with a

heteroleptic multiple bond between heavier main-group elements have attracted

considerable attention particularly those between group 14 and 15 elements this is


- 58 -

attributed to the pronounced polarity of the E14-E15 multiple bonds[124]

Phosphasilene

containing Si-P double bonds is an analogous of iminosilane The first isolable

phosphasilene with a three coordinate Si and a two coordinate P atom was reported by

Bickelhaupt and coworkers (Scheme 321) in 1984[125]

and several other similar

species containing localized and delocalized Si=P bonds were synthesized and

structurally characterized in the later period[126]

Their rich chemistry provides new

approaches to functional Si-P compounds

Furthermore the more challenging phosphasilyne with a silicon-phosphorus triple

bond (Scheme 321) is heretofore unknown[127]

this is mainly due to the high

tendency of the highly polarized Si-P multiple bonds to dimerize or even

oligomerize[126c]

However the availability of elusive phosphasilyne species would be

a strongly desired progression with respect to the synthesis of polyfunctional silicon-

phosphorus containing materials from it By spatial protection of a Si-P multiple bond

through the steric hindrance by suitable bulky substituents the oligomerization of the

highly polarized Si-P multiple bonds could be prevented additionally to the benefit of

the donor-acceptor stabilization of Si-P multiple bonds

Scheme 321 The first phosphasilene (left) and phosphasilyne (right)

Imaginable methods to synthesize a phosphasilyne employing corresponding

precursors comprise oxidation of bis-silylene 30a with elemental phosphorus and

elimination of phosphino silane 30b (Scheme 322) Whether the phosphasilyne 30c is

available depends only on the spatial andor donor-acceptor protection of bulky ligand

L Now there are not many choices of silicon compounds with very bulky ligand L

that are suitable for preparation of phosphasilynes Our current attempt was on the


- 59 -

way towards phosphasilyne employing amidinato ligand stabilized chlorosilylene

aLSiCl

[31a] However the isolated dimerized product was the unique 24-disila-13-

diphosphacyclobuta-13-diene (aLSiP2Si

aL) 31

[128] starting from the new N-

heterocyclic bis(trimethylsilyl) phosphino silylene precursor 30[128]

Scheme 322 Imaginable methods towards a phosphasilyne

341 Synthesis of N-heterocyclic phosphino silylene 30

The starting material bis(trimethylsilyl)phosphanyl silylene 30[128]

was easily

accessible in 83 yield by salt elimination reaction of N-heterocyclic chlorosilylene

26[31a]

with the corresponding lithium phosphide LiP(SiMe3)2 at room temperature

(Scheme 323) The 1H-NMR spectrum exhibits one singlet at δ = 058 ppm for methyl

of silyl and another singlet at δ = 124 ppm for methyl of NtBu as well as one set of

resonances for the Ph group of the amidinate ligand in the region of 681-741 ppm

The 29

Si-NMR spectrum of 30 shows two sets of doublet at δ = 229 ppm for silicon

of silyl and at δ = 1943 ppm for silicon of silylene The latter is much downfield

shifted than that of previously reported aLSi-P

iPr2 derivative (562 ppm)

[31b] One

singlet at δ = -221 ppm was found by 31

P-NMR measurement which exhibits a

tremendous upfield shift when compared with that of aLSi-P

iPr2 derivative (-165

ppm)[31b]


- 60 -

Scheme 323 Synthesis of N-heterocyclic phosphino silylene 30

The molecular structure of 30 was also substantiated by single-crystal X-ray

diffraction analysis (Figure 315) The molecule 30 contains triply coordinate Si and P

atoms and two lone pairs at the Si and P center respectively The Si and P center

display a distorted trigonal pyramidal geometry The sum of bond angles is 33071deg at

the P center and 27762deg at the Si center The latter is consistent with that (2765deg) of

aLSi-P

iPr2 The angle of N(2)-Si(1)-P(1) (10854(8)deg) is larger than that of N(1)-Si(1)-

P(1) (9998(9)deg) Si-N distances of 1877(3) and 1882(2) pm in 30 are comparable to

those (1875(1) pm and 1881(1) pm) of the aLSi-P

iPr2 derivative

[31b] The Si1-P1

distance of 30 (22838(12) pm) is slightly shorter than the Si-P bond length (2307(8)

pm) in the aLSi-P

iPr2 derivative and the elongated P1-Si2 and P1-Si3 single bonds in

30 (22264(13) and 22321(12) pm) reflect steric congestion within the P(SiMe3)2

subunit



(pm) and angles (deg) P1-Si1 22838(12) P1-Si2 22264(13) P1-Si3 22321(12)

Si1-N1 1877(3) Si1-N2 1882(2) Si2-P1-Si3 10859(5) Si2-P1-Si1 103905


- 61 -

Si3-P1-Si1 11822(5) N1-Si1-N2 6910(11) N1-Si1-P1 9998(9) N2-Si1-P1

10854(8)


Since the phosphanyl silylene 30 was successfully accessed bearing a SiMe3 as

reactive leaving-groups at phosphorus[129]

its suitability as a precursor for the

formation of a phosphasilyne was probed Because of the labile nature of the P-SiMe3

bonds in 30 the compound was exposed to dichlorotriphenylphosphorane Ph3PCl2 as

a promising smooth oxidant for desilylation with the intention to produce the desired

phosphasilyne along with Me3SiCl and PPh3 Surprisingly the reaction of 30 with one

molar equiv of Ph3PCl2 in toluene at room temperature led to the formation of the

unique compound 31[128]

(Scheme 324) which could be isolated as yellow crystals in

72 yield

Scheme 324 Synthesis of Si2P2-cycloheterobutadiene 31

Compound 31 represents a dimerized form of the desired phosphasilyne and was

fully characterized by means of multinuclear NMR spectroscopy and single crystal X-

ray diffraction analysis The 1H-NMR spectra of 31 displays a singlet for the

tBu

groups at δ = 135 ppm and one set of resonances for the Ph groups in the ldquoaromaticrdquo

region The triplet signal in the 29

Si-NMR spectrum of 31 at δ = 265 ppm (1JSiP = 998

Hz) indicates that two P atoms are bonded to silicon center Meanwhile the more

deshielded (ca 46 ppm) singlet resonance at δ = -1649 ppm in the 31

P-NMR spectrum

compared to that in 30 is in accordance with the four-membered ring structure of 31


- 62 -

bearing two polarized Si-P π-bonds

The result of the X-ray diffraction structure analysis is in accordance with that of

NMR spectroscopy which confirms that 31 is a 24-disila-13-diphosphacyclobuta-

13-diene (Figure 316) The Si2P2 core in 31 has a planar diamond-shaped geometry

and possesses two-coordinated P atoms and four-coordinated Si atoms each with a

dative NrarrSi bond The Si-P bonds lengths in 31 are 21701(12) and 21717(11) pm

respectively which are in the range of a Si=P double bond length (2095(3) pm) in the

Phosphasilene[128]

and the Si-P single bond length of 30 (22838(12) pm) this

indicates σ- and π-electron resonance stabilization within the Si2P2 cycle which has

been confirmed by theoretical calculations (see p 64) Of note the transannular

Si1middotmiddotmiddotSi1rsquo (25626 pm) is shorter than the Si-Si distance of disilacyclopropene[130]

(tBu3Si)2SiSi(Si

tBu3)C-Ad (Ad = adamantyl) (25797(8) and 25991(9) pm) and hexa-

tert-butyldisilane tBu3Si-Si

tBu3 (2697(9) pm) and the P1middotmiddotmiddotP1rsquo (3505 pm)

separations in 31 is much larger than that for P-P bonds observed in tetrahedral

elementary phosphorus P4 (221 pm)[131]

Evidently the peculiarly short Si1middotmiddotmiddotSi1rsquo

distance is caused by the geometric constraints of the Si1-P1-Si1rsquo and endocyclic P1-

Si1-P1rsquo angles of 7234(4)deg and 10766(4)deg respectively and not driven by attractive

Si1-Si1rsquo interaction



(pm) and angles (deg) P1-Si1 21701(12) P1-Si1rsquo 21717(11) Si1-N1 1858(3)

Si1-N2 1856(2) Si1-P1rsquo 21717(11) Si1-Si1rsquo 25626(16) Si1-P1-Si1rsquo 7234(4)

N2-Si1-N1 7078(11) P1-Si1-P1rsquo 10766(4)


- 63 -

The formation of 31 in a multistep which is depicted in Scheme 325 was proposed

Firstly formation of the corresponding chloro-(silyl)phosphanyl silylene intermediate

31a is conducted by cleavage of one of the Si-P bonds of the P(SiMe3)2 subunit with

Ph3PCl2 Subsequently elimination of Me3SiCl from 31a occurs to give the reactive

intermediate 31b which could be treated as a silylene-phosphinidene (Scheme 325

right) or a phosphasilyne (Scheme 325 left) further dimerization of intermediate 31b

affords the isolated product 31 A similar dimerization process has been proposed by

Wiberg for disilynes (SiequivSi) as reactive intermediates to produce

tetrasilatetrahedranes[132]

To elucidate the reason for the formation of 31 preferred over its hypothetical Si2P2-

tetrahedranceisomer 31d (Scheme 326) we performed DFT calculations of 31 and

disiladiphosphatetrahedranes 31d The result shows that 31d is much less stable than

compound 31 with 462 kcalmiddotmolminus1

higher in energy which is in agreement with the

experimental result Compound 31 with a planar structure is most likely stabilized by

the dative NrarrSi coordination of the bulky amidinato ligands Meanwhile this also

leads to a shorter Si-N bond length that is 1856(2) and 1858(3) pm in 31 are shooter

than those (1877(3) pm and 1882(2) pm) of in 30 and also those of in chlorosilylene

aLSiCl (1870(2) pm and 1917(2) pm)

[31a] Furthermore this NrarrSi donor

stabilization could demonstrate an ylide-like electronic structure of 31 (Scheme 326)



- 64 -

Scheme 326 Resonance structures of 31

In order to unravel the electronic configuration of 31 DFT calculations at

B3LYP6-31G(d) level using the parameters obtained from X-ray diffraction as the

initial structure were performed[101c 119]

The optimized structure matched the

experimental data of 31 very well According to the NPA charges each Si atom in the

Si2P2-ring has a large positive net charge (+1204) while as expected P atoms in the

ring bear slight smaller negative charges (-0765) Meanwhile HOMO-5 of 31 shows

a set of Si-P σ-bonding orbitals (Figure 317 left) whereas the HOMO-2 contains

mainly the delocalized two π-bonding orbitals (Figure 317 right) Accordingly a

NBO analysis indicates that the Si2P2-core of 31 bears a Lewis structure with four

occupied σ-bond orbitals for the Si-P bonds (1917e for Si1-P1 1916e for Si1-P1rsquo

1916e for Si1rsquo-P1 and 1918e for Si1rsquo-P1rsquo) along with two filled Si-P π-bond

orbitals with 1770e for the Si1- P1 and Si1rsquo-P1rsquo π-bonding interaction respectively

The latter canonical π-bond orbitals are strongly polarized toward the P atoms

(8753 at the P and 1247 at the Si) Likewise the WBI (Wiberg Bond Index)

values of the Si-P bonds (1142 and 1140) are higher than that of the phosphino

silylene 30 (0920)

Figure 317 Molecular orbitals of 31 representing the presence of σ-electron and π-

electron delocalization within the Si2P2 cycle HOMO-5 (left) and HOMO-2 (right)


- 65 -

According to the aforementioned betaine (ylide)-like resonance stabilization 31

totally differs from cyclobuta-13-diene derivatives The calculations of the nucleus

independent chemical shift[92]

(NICS) also supports this conclusion The result of

NICS reveals negative values (NICS(1) = -257 and NICS(0) = -601 ppm) indicating

that 31 has a somewhat aromatic character which is opposite to the properties of

cyclobuta-13-dienes that are antiaromatic As a summary the results of theoretical

calculations are in agreement with the idea to describe 31 as the ylide-like resonance

structure 31c with some contribution of the resonance forms As a result the smaller

endocyclic angle at phosphorus than that at silicon is contributed by the repulsion

between the negatively charged P atoms

35 Isolation of an aminosilylene-stannylene dichloride 33

Nucleophilic and electrophilic properties of Si Ge and Sn metallylenes were

discussed in chapter 32 (see p 46) Due to the strong donor property of the carbene

lone pair in coordination to empty p-orbital of low valent Si Ge Sn atom centers

some carbene stabilized divalent Si Ge Sn halides could be synthesized in the last

twenty years[28 44 133]

There is also a great interest to find mixed Si Ge Sn

metallylene-metallylene complexes in which one metallylene is stabilized through the

lone pair coordination of another one In the following the synthesis of the first

example of a silylene stabilized SnCl2 complex will be shown

The dimeric micro-chlorotin(II) amides 32[53]

(I44 in Introduction) was identified as

useful candidate for the generation of such an example The synthesis of

bis(trimethylsilyl)amino-tin chloride ((Me3Si)2N-SnCl)2 32 is shown in Scheme 327

Bis(bis(trimethylsilyl)amino)2tin(II) ((Me3Si)2N)2Sn 32a could be prepared in good

yield by the double lithioamination of SnCl2 with LiN(SiMe3)2 in a 1 2 ratio[47a]

The


- 66 -

same reaction but with one molar equiv of LiN(SiMe3)2 gives the monosubstituted

product 32 It was also easily accessible by amino chlorine exchange between

((Me3Si)2N)2Sn and SnCl2 in a 11 ratio[53]

(Scheme 327)

Scheme 327 Synthesis of micro-chlorotin(II) amide 32

The dimeric structure of 32 can be splited by treatment with Lewis base for

example Si Ge Sn metallylenes In order to synthesize a silylene coordinated

stannylene chlorosilylene 26 was mixed with micro-chlorotin(II) amide 32 in toluene A

logical intermediate 33a is proposed here as an inevitable intermediate (Scheme 328)

At first chloro bridges are opened because of the coordination of silylene 26 to create

33a Then via amino chlorine exchange product 33 becomes accessible From a

saturated hexane solution at low temperature the silylene-stannylene dichloride 33

was isolated as colorless crystals in 49 yield The product 33 was determined by X-

ray diffraction analysis and elemental analysis Owing to the unstable nature of

silylene and tin dichloride coordination bond (Si rarrSn) 33 decomposed in a grey

mixture powder of amino silylene also-N(SiMe3)2

[33d] and SnCl2 after isolation from

solvent in vacuum 1H-NMR spectrum shows only resonances of amino silylene in

good agreement with the reported compound[33d]

Scheme 328 Synthesis of aminosilylene-stannylene dichloride 33

According to X-ray diffraction analysis compound 33 represents the first example

of silylene stabilized SnCl2 complex The molecular structure of 33 (Figure 318)


- 67 -

exhibits a trigonal pyramidal geometry on Sn and a distorted tetrahedral configuration

of Si The Cl-Sn-Cl angle is 9400(9)deg and the sum of bond angles at the Sn center is

2820deg The SirarrSn distance (2740(2) pm) is longer than the Si-Sn bond lengths

(2622(2) and 2641(2) pm) in the silyl stannane compound[134]

(Scheme 329) The

Sn-Cl distances of 2468(3) and 2473(3) pm in 33 are comparable to those in a

carbene-stannylene complex (2456(2) and 2458(2) pm) (Scheme 329)[133b]

Si-N

distances of 1832(7) and 1827(7) pm in 33 are somewhat shorter than those of

phosphanyl silylene 30 (1877(3) and 1882(2) pm) and amino silylene (18780(10)

and 18776(10) pm) which is the remaining molecule of 33 without SnCl2[33d]

Scheme 329 A silyl stannane[134]

(left) and a carbene-stannylene complex[133b]

(right)



(pm) and angles (deg) Sn1-Si1 2740(2) Sn1-Cl1 2468(3) Sn1-Cl2 2473(3) Si1-

N1 1832(7) Si1-N2 1827(7) Si1-N3 1705(7) Si2-N3 1780(7) Si3-N3

1791(8) Cl1-Sn1-Cl2 9400(9) Cl1-Sn1-Si1 9886(8) Cl2-Sn1-Si1 8914(7)

Sn1-Si1-N3 1252(3) N2-Si1-N1 722(3) Si1-N3-Si2 1172(4) Si1-N3-Si3

1248(4) Si2-N3-Si3 1179(4)


- 68 -

36 Exploration and property of SiCSi pincer bis-silylene 34

Because of the feasible structural tuning with many choices of donor groups a

general overview of pincer arenes was introduced (Introduction p 19) Compounds of

type 35a having a pincer-like skeleton are depicted in Scheme 330 They represent

promising new types of pincer ligands which could coordinate with a metal by facile

C-H activation in the ortho-position Although many bis-metallylenes are accessible

(see Introduction 13) pincer ligands containing divalent heavier group 14 elements

are new in the field of synthetic inorganic chemistry At the same time the desired

pincer arenes 35a could serve as much stronger σ-donor ligand towards transition-

metals than traditional phosphane ligands[70 79b c 122]

Up to now only a few isolable

spacer separated bis-silylenes with two divalent silicon centers are known these

include bis-silylene oxide 28[32a]

in this work and bis-silylenes I42[52]

I58[61]

and

I64[65]

(in Introduction p 12-15) Inspired by these results the synthesis of a

silicon(II)-based pincer ligand 35a appeared attractive and its coordination property

towards transition-metals should be investigated

Scheme 330 Low-valent group 14 metallylene-based ECE pincer arenes

361 Synthesis of the first bis-silylene-based SiCSi pincer arene 35

Scheme 331 shows the synthetic route for the first attempt towards a bis-silylene-

based SiCSi pincer arene 35d The phenolation of trichlorosilane was readily

accessible to disilane 35b in hexane Reaction of 35b with two molar equiv of lithium


- 69 -

amidinate 25 in diethylether gave the amidinate substituted disilane 35c The bis-

silylene pincer arene 35d was not easily separable by the following dehydrochloration

of 35c employing two molar equiv of LiN(SiMe3)2 in toluene Products seemed a

complicated silylene-LiCl mixture which was not soluble in toluene or diethylether

The desired bis-silylene pincer arene could not be isolated from mixtures

Scheme 331 The first attempt towards a bis-silylene-based SiCSi pincer arene 35d

But the synthesis of SiCSi pincer arene 35 could be achieved through the protocol

in Scheme 332 Dilithiation of 46-di-tert-butylresorcinol with nBuLi furnishes the

corresponding 13-dilithium resorcinolate 34 After a salt metathesis reaction with the

N-donor stabilized chloro silylene 26[32b]

in the molar ratio of 12 the desired

compound 35[33b]

could be isolated as pale yellow crystals in 79 yield The

constitution and composition of SiCSi pincer arene 35 was elucidated by 1H-

13C-

and 29

Si-NMR spectroscopy and elemental analysis

Scheme 332 Synthesis of SiCSi pincer arene 35

The 1H-NMR spectrum of 35 exhibits one singlet for the N


ppm and one singlet for CtBu groups at δ = 174 ppm and one set of resonances for the

Ph groups of the amidinate ligands Almost identical variable-temperature (VT) 1H-

NMR spectra of 35 in C7D8 in the temperature range of 210 to 320 K indicate


- 70 -

relatively low rotation barriers of the Si-O bonds on the NMR time scale A sharp

singlet in the 29

Si-NMR spectrum at δ = -240 ppm is comparable to that observed for

alkoxy-substituted silylenes aLSiOR (R =

tBu

iPr)

[31b]

The molecular structure of 35 could be confirmed by a preliminary single-crystal

X-ray diffraction analysis but a discussion of metric parameters was not possible

because of the moderate crystal quality Still it is clear that the two silylene-like

moieties in 35 face in the almost same direction (Figure 319) To get more

information about the molecular structure of 35 DFT calculations [B3LYP6-

31G(d)][101c 119]

were performed by Shigeyoshi Inoue (TU Berlin) The geometry of 35

obtained by X-ray crystallographic analysis was used as the initial structure The

optimized structure of 35e and 35ersquo is displayed in Figure 320 The Si1-O1-C1 angle

(14179deg) is larger than that of Si2-O2-C3 (13217deg) While the dihedral angle of Si1-

O1-C1-C2 is 2437deg the dihedral angle of Si2-O2-C3-C2 is 039deg

Figure 319 Molecular structure of 35 Hydrogen atoms are omitted for clarity X-

ray data are not sufficient for discussion

The Si-O single bond distances of 17056 and 17190 pm are little longer than those

of bis-silylene oxide 28[32a]

(1641(2) and 1652(2) pm) and alkoxysilylenes aLSiOR

(R = tBu

iPr)

[31b] (16442(3) and 16501(2) pm) due to steric hindrance The C2-


- 71 -

symmetric rotational isomer 35ersquo was identified as a stable form on the hyperpotential

energy surface with a slightly lower energy of 75 kJsdotmolminus1

Interestingly the Si-O

distance of 35ersquo is little longer than those of 35e The bond rotation barrier of the Si-O

bonds in 35e and 35ersquo is similar and estimated to be +334 kJsdotmolminus1

by theoretical

calculation

Figure 320 Optimized structures of bis-silylene SiCSi pincer ligand 35e (left) and

its rotational isomer 35ersquo (right) at the B3LYP6-31G(d) level Hydrogen atoms are

omitted for clarity Selected bond lengths (pm) and angles (deg) of 35e and 35ersquo

compound 35e Si1-O1 17056 Si2-O2 17191 Si1-O1-C1 14179 Si2-O2-C3

13217 compound 35ersquo Si1-O1 17294 Si2-O2 17294 Si1-O1-C1 13028 Si2-

O2-C3 13028

362 Formation of SiCSi pincer arene PdII

complex 36

Although bis-silylene 35 bearing an amidinate ligand may not serve as a π-acceptor

it was a strong σ-donor ligand To investigate the pincer-type coordination ability of

35 its reactivity towards phosphine palladium(0) complexes was evaluated Treatment

of 35 with 05 equiv of tetrakis(triphenylphosphine)-palladium Pd(PPh3)4 in hexane

at room temperature afforded the novel silylene-silyl(phenyl)palladium(II) complex

36[33b]

as sole product which could be isolated as orange crystals in 81 yield

(Scheme 333)


- 72 -

Scheme 333 Formation of 36 from reaction of 35 with Pd(PPh3)4

A different type of silyl-silylene metal complexes has been described by Ogino and

co-workers[66b c 78]

Compound 36 was fully characterized by multinuclear NMR

spectroscopy and single crystal X-ray diffraction analysis The structure of 36

indicates that two equivalents of 35 were consumed With a 11 molar ratio of starting

materials the yield of 36 decreased (asymp30) but still no other product or intermediate

could be detected by 1H-NMR spectroscopy

The molecular structure of 36 is shown in Figure 321 Remarkably compound 36

crystallizes as racemic mixture of its R and S enantiomers of which only the S form is

presented here The PdII atom has a typical distorted square-planar configuration

defined by the two silylene SiII atoms Si2 and Si3 the silyl Si

IV atom Si1 and the

carbon atom C1 of the central aryl ring Interestingly there is a 12-hydride shift from

palladium to silicon during the complexation forming a Si-H silyl group which breaks

the former Si1-N2 bond in 35 Due to coordinative saturation of the Pd center one

silylene subunit (Si4) remains ldquofreerdquo The bent Si3-Pd1-C1 angle of 16783(12)deg in 36

is contrary to the linear X-Pd-C (X = Cl I Ph 4-fluorophenyl OCOCF3 etc) angles

of reported palladium(II) complexes supported by a PCP type pincer arene ligand[72b

77 135] The Si1-Pd1-Si2 angle of 15503(4)deg deviates from the linear alignment and is

smaller than the respective P-Pd-P angle of the PCP pincer-type palladium

complex[72b 77 135]

The silylene PdII dative bond lengths (Si2-Pd1 23271(12) and

Si3-Pd1 23038(11) pm) of 36 are shorter than that of the Si1-Pd1 distance


- 73 -

(23561(12) pm) illustrating the difference between a silyl ligand (Si1) with a SiIV

-Pd

single bond vs a silylene ligand (Si2 and Si3) with a SiII-Pd dative bond However

the Si2-Pd1 and Si3-Pd1 distances in 36 are somewhat longer than those of

silylenerarrpalladium complexes[136]

(224 and 226 pm) from Kira (Scheme 334)

Furthermore Pd1-C1(aryl) bond length of 36 (2125(3) pm) is longer than those of

reported PCP pincer-type palladium(II) complexes (Pd-C distance 197-203 pm)[135a-e

135g] presumably because of steric congestion

Scheme 334 Silylenerarrpalladium complexes from Kira[136]

Figure 321 Molecular structure of 36 Only the S form of racemic mixture is

shown Thermal ellipsoids are drawn at a probability level of 30 Hydrogen atoms

are omitted for clarity except for the H1 atom Selected bond lengths (pm) and

angles (deg) Pd1-C1 2125(3) Pd1-Si1 23561(12) Pd1-Si2 23271(12) Pd1-Si3

23038(11) Si1-O1 1694(3) Si1-N1 1789(4) Si2-O2 1675(3) Si2-N5 1862(3)

Si2-N6 1840(4) Si3-O3 1662(3) Si3-N7 1888(3) Si3-N8 1860(3) Si4-O4

1704(3) Si4-N3 1893(4) Si4-N4 1892(4) Si1-Pd1-Si2 15503(4) Si1-Pd1-C1

Si2Si1

C1

Pd

Si3

213 pm

233 pm236 pm

230 pm

O1 O2


- 74 -

7861(11) Si2-Pd1-C1 7681(11) Si3-Pd1-C1 16783(12)

The 1H-NMR spectrum of 36 shows twelve sets of nonequivalent

tBu groups

which agrees with its crystallographic analysis Moreover the resonance for the Si-H

proton is observed at δ = 659 ppm The 29

Si-NMR spectrum of 36 in C6D6 displays

four signals at δ = minus87 (aLSi Si4) 397 (HSi Si1) 623 and 658 ppm (SirarrPd Si2

and Si3) respectively The chemical shift of the Si1 atom (SiIV

-H) has moved upfield

comparable to those of a related HSirarrPd complex reported by Kira Iwamoto and co-

workers because of the electronegative N and O atoms bound to the Si1 atom[136a]

The 29

Si resonances of the two SiII atoms (Si2 Si3) coordinated to the palladium

center are similar to those of other amidinate-based silylene transition-metal

complexes[71 137]

and significantly shifted to higher field in comparison to those

reported for donor-free silylene palladium complexes owing to the additional N-donor

coordination of the amidinate ligand to the SiII atom Additionally the infrared

spectrum of 36 shows a weak Si-H stretching vibration band at 2135 cmminus1

The

observed stretching frequency of 36 is higher than those of other reported palladium

hydridosilyl complexes (2008ndash2121 cmminus1

)[135c 135f 136a]

363 DFT calculation for explanation of reaction mechanism

To investigate the uncommon reactivity of 35 towards Pd(PPh3)4 quantum

chemical calculations using density functional theory (DFT) at the B3LYP level using

6-31G(d) basis set for H C N O P and Si atoms and the LANL2DZ level for the Pd

atom with the Gaussian 03 program for model compounds 36andash36e were performed

by Shigeyoshi Inoue (TU Berlin)[101c 119]

A schematic representation of the potential

energy surface of the proposed pathway for the formation of 36 is given in Scheme

335


- 75 -

Scheme 335 DFT-derived relative energies of model compounds 35a-35e

From this it was assumed that stepwise dissociation of phosphine ligands of

Pd(PPh3)4 forms 36a as the initial intermediate by the insertion reaction of Pd0 into

the pincer C-H bond of the central aryl ring of 35 Subsequently the 16-valence

electron PdII complex 36a undergoes a 12-hydride shift from palladium to a silicon(II)

donor atom to form the 14-valence electron silylene silyl(aryl)palladium(II) complex

36c as second intermediate The latter process occurs through transition state 36b-TS

with a barrier of +878 kJsdotmolminus1

and 36c is only 67 kJsdotmolminus1

more stable than 36b-TS

The electron-deficient PdII complex 36c readily undergoes coordination with

phosphine ligand or silylene donor moiety of ldquofreerdquo 35 leading to the formation of

more stable 16-electron complexes According to that the calculated relative energies

of PrarrPd complex 36d stabilized by PPh3 and SirarrPd complex 36e stabilized by

methoxy silylene aLSiOMe as model silylene donor are +380 and minus176 kJsdotmol

minus1

respectively Since SiII of intramolecular N-donor stabilized silylenes is a stronger σ-

donor than PIII

of phosphines complex 36e is 556 kJsdotmolminus1

more stable than 36d

Overall the stepwise transformation of 36a into 36e in the presence of PPh3 and the

model silylene aLSiOMe is exothermic by 176 kJsdotmol

minus1


- 76 -

37 Bis(silylenyl)- and bis(germylenyl)-substituted ferrocenes

After successful isolation of the first bis-silylene oxide 28[32a]

and the first bis-

silylene pincer arene 35[33b]

in order to obtain other new bis-silylene(germylene) as

potential bidentate σ-donor ligands the novel type of bis-silylene(germylene) with a

ferrocendiyl spacer which could result in unique properties was investigated The

facile synthesis of the first bis(silylenyl)- and bis(germylenyl)-substituted ferrocenes

aLSi-Fc-Si

aL 38 (Fc = ferrocendiyl) and

aLGe-Fc-Ge

aL 40 respectively as well as

their corresponding cobalt and iron complexes could be realized in the course of this

PhD thesis[33a]

371 Synthesis of bis(silylenyl)- and bis(germylenyl)-ferrocenes 38 and 40

Since the reaction of chlorosilylene 26[32b]

with dilithium resorcinolate 34 afforded

the SiCSi pincer bis-silylene 35 was assumed that chlorosilylene 26 and


(aLGeCl) could be suitable precursors for the desired bis-

metallylene functionalized ferrocenes Ferrocene with nBuLi and TMEDA

(tetramethylethyldiamine) in hexane gave 11rsquo-dilithioferrocene 37[138]

quantitatively

Subsequently treatment of chlorosilylene 26 with 11rsquo-dilithioferrocene 37 led to the

formation of bis-silylene 38[33a]

in 70 yield (Scheme 336) Similarly

bis(germylenyl)-ferrocene 40[33a]

could be isolated in 77 yield by salt metathesis

reaction of 11rsquo-dilithioferrocene 37 with chlorogermylene 39 The structures of 38

and 40 were determined by multinuclear NMR spectroscopy elemental analysis mass

spectrometry and X-ray crystallographic analysis (only for compound 40)

1H-NMR spectra of compound 38 and 40 are very similar They exhibit a singlet for

four tBu groups (38 δ = 116 ppm 40 δ = 111 ppm) Two sets of hyperfine coupled

triplet (38 δ = 451 and 472 ppm 40 δ = 461 and 471 ppm) are assigned to the

protons of ferrocene The resonance of the Ph protons (38 and 40) appears in aromatic


- 77 -

resonance region from 690 to 717 ppm Accordingly the 13

C-NMR spectra of 38 and

40 each show three resonances for the ferrocendiyl moieties (38 δ = 709 727 and

846 ppm 40 δ = 701 723 and 920 ppm) Furthermore bis-silylene 38 gives rise to

a singlet at δ = 433 ppm in the 29

Si-NMR spectrum

Scheme 336 Synthesis of bis(silylenyl)- and bis(germylenyl)-ferrocenes 38 40

Single crystals of 40 suitable for an X-ray single crystal analysis were obtained

from hexane solution The crystals of 40 consist of two conformational isomers as

shown in Figure 322 Two molecular structures of 40 confirm that the two N-donor-

stabilized germylene moieties are bonded to C1 and C7 (endo-configuration) or C8

(exo-configuration) of the ferrocendiyl spacer Distances of Ge1-C1 and Ge2-C7 in

40-endo are 1979(9) and 1983(11) pm while distances of Ge1-C1 and Ge2-C8 in 40-

exo are 1991(2) and 19774(19) pm respectively The Ge-N bonds (2006 to 20402

pm) of two isomers are slightly shorter than those of precursor 39[41]

The GeII centers

in 40 adopt a pyramidal geometry with the sums of bond angles of 25593deg and

25669deg for 40-exo 2591deg and 2546deg for 40-endo respectively The structural feature

of the amidinate ligands in 40 is reminiscent of those reported for related bis-

germylenes such as I63[64]

(aLGe-NPh)2 and I75 I76 LGe-X-GeL (X = O S L =

tBuC(N-Dip)2)

[67] The isolation of two conformational isomers of 40-exo and 40-endo

indicates a small rotating energy of the functional ferrocendiyl That means bis-

germylene 40 and bis-silylene 38 don not need more activation energy serving as

bidentate ligand


- 78 -

Figure 322 Molecular structures of 40-endo (top) and 40-exo (bottom) Thermal

ellipsoids are drawn at a probability level of 30 Hydrogen atoms are omitted for

clarity Selected bond lengths (pm) and angles (deg) for 40-endo (top) Ge(1)-C(1)

1979(9) Ge(2)-C(7) 1983(11) Ge(1)-N(1) 2027(8) Ge(1)-N(2) 2006(8)

Ge(2)-N(3) 2022(7) Ge(2)-N(4) 2037(7) C(1)-Ge(1)-N(2) 983(3) C(1)-Ge(1)-

N(1) 955(3) N(2)-Ge(1)-N(1) 653(3) C(7)-Ge(2)-N(3) 953(4) C(7)-Ge(2)-

N(4) 941(4) N(3)-Ge(2)-N(4) 652(3) for 40-exo (bottom) Ge1-C1 1991(2)

Ge2-C8 19774(19) Ge1-N1 20261(16) Ge1-N2 20247(17) Ge2-N3

20402(15) Ge2-N4 20162(16) C1-Ge1-N1 9662(7) C1-Ge1-N2 9445(7) N1-

Ge1-N2 6486(7) C8-Ge2-N3 9492(7) C8-Ge2-N4 9716(7) N3-Ge2-N4

6459(6)

The molecular structure of bis-silylene 38 has been ambiguously determined by X-

ray single crystal diffraction The structural feature of 38 is very similar to that of 40-

exo isomer However the X-ray data are not sufficient for any further discussion

(Figure 323)


- 79 -

Figure 323 Molecular structure of 38 X-ray data are not sufficient for discussion

The mass spectrometry confirmed the composition of 38 (Figure 324) The (ESI)

mass spectrum of 38 is dominated by a peak at mz 703329 which can be attributed to

the protonated molecular ion [38+H]+ Isotopic distribution of molecular peaks

demonstrates a good agreement with calculated mass composition The comparison of

experiment and calculation confirms the presence of bis-silylenyl substituted

ferrocene molecules

6 9 0 6 9 5 7 0 0 7 0 5 7 1 0 7 1 5 7 2 0

m z

0

1 0

2 0

3 0

4 0

5 0

6 0

7 0

8 0

9 0

1 0 0

0

1 0

2 0

3 0

4 0

5 0

6 0

7 0

8 0

9 0

1 0 0

Re

lative

Abu

nda

nce

7 0 3 3 2 9

7 0 4 3 3 2

7 0 5 3 3 47 0 1 3 3 4

7 0 6 3 2 96 9 0 2 4 9 6 9 5 2 2 5 7 1 7 3 4 57 1 0 4 7 3

7 0 3 3 3 1

7 0 4 3 3 4

7 0 5 3 3 87 0 1 3 3 6

7 0 6 3 3 17 1 0 3 3 5

N L 3 1 3 E 7

W Y-F e S i2 _ S p ri tze 1 -2 9 R T 0 0 0 -0 7 7 A V 2 9 T F T M S + c E S I F u ll m s [1 0 0 0 0 -2 0 0 0 0 0 ]

N L 4 9 7 E 5

C 4 0 H 5 4 F e N 4 S i 2 + H C 4 0 H 5 5 F e 1 N 4 S i 2

p a C hrg 1

Figure 324 Experimental (top) and simulated (bottom) ESI-MS spectra of 38

Compounds 38 and 40 represent the first examples of isolable silylene- and

germylene-substituted ferrocenes respectively Alternative example of SiII-ferrocene


- 80 -

compound is a disilene-functionalized ferrocene reported by Tokitoh and co-workers

recently[139]

However disilene derivates belong essentially to another type of low-

valent silicon compounds in comparison to triply coordinated silylenes Instead of

conjugated electronic effect of disilene-ferrocene system the ferrocene bridged bis-

silylene or bis-germylene system could have better chelating σ-donor character It is to

confirm in a coordination chemistry of bis-silylene 38 and bis-germylene 40 with

transition-metals

372 Formation of CoICp complexes with 38 and 40

In order to investigate the coordination ability of 38 and 40 toward transition-

metals and inspired by the reactivity of bis-silylenes 28 and 35 toward Ni0 and Pd

0[32a

33b] as well as by reports on spacer-separated bis-germylene molybdenum chelated

complex I65-Mo[66b]

(see Introduction p 18) firstly the coordination behavior of

potentially bidentate ligands 38 and 40 towards CoICp complex fragments

[140] was

examined A suitable CoICp source is accessible by treatment of CoBr2 with sodium

cyclopentadienide (NaCp) and potassium graphite (KC8) in tolueneTHF 41 mixture

resulting in the generation of (CpCoILn) (L = toluene or THF) in solution Reaction of

thus-formed CoICp species with bis-silylene 38 yielded the desired bis-silylene Co

I

complex 41[33a]

in 30 yield (Scheme 337) Similarly bis-germylene CoI complex

42[33a]

has been successfully synthesized from 40 and isolated in 61 yield

Scheme 337 Synthesis of bis-silylene and bis-germylene CoICp complexes 41 and 42


- 81 -

In comparison to bis-silylene 38 and bis-germylene 40 1H-NMR spectra of

compound 41 and 42 show an additional singlet for protons of CoICp group (41 δ =

496 ppm 42 δ = 504 ppm) A singlet for four tBu-groups appears at δ = 111 ppm by

bis-silylene Co-complex 41 and at δ = 139 ppm by bis-germylene Co-complex 42

Two sets of hyperfine coupled triplet (41 δ = 440 and 461 ppm 42 δ = 438 and

459 ppm) are assigned to protons of ferrocene The resonance of phenyl protons (41

and 42) appears in aromatic resonance region In the 13

C-NMR spectra of 41 and 42

each exhibit one resonance for carbons of CoICp (41 δ = 780 ppm 42 δ = 759 ppm)

and three resonances for the ferrocendiyl moieties (41 δ = 700 745 and 851 ppm

42 δ = 699 737 and 891 ppm) In the 29

Si-NMR spectrum the coordination of the

bis-silylene moieties to the Co atom results in a drastic downfield shift of the

resonance of 41 (δ = 820 ppm) in comparison to situation of 42 (δ = 433 ppm)

Isolated products 41 and 42 are first heterobimetallic complexes of CoICp with bis-

silylene or bis-germylene in a chelating fashion The molecular structures of 41 and

42 (Figure 325) were determined by single-crystal X-ray diffraction analyses In both

complexes cobalt is coordinated one side by cyclopentadienyl and another side by bis-

silylene 38 or bis-germylene 40 and contains 18 valence electrons Angles of Si1-Co1-

Si2 and Ge1-Co1-Ge2 are 9389(5)deg and 9279(2)deg respectively

The silicon atoms in complex 41 and germanium atoms in complex 42 are four

coordinated and show a distorted tetrahedral geometry The Co-Si bond lengths of 41

(21252(14) and 21200(14) pm) are similar to that in chlorosilylene CoICp(CO)

complex 41a[141]

(21143(4) pm) Furthermore the Co-Si bonds of 41 are shorter than

the Co-Si distances in dichlorosilylene-CoICp(CO) complex 41b

[142] (21348(5) pm)

in dichlorosilylene-Co(CO)3+ cationic complex 41c

[143] (2228(2) pm) in

chlorosilylene Co(CO)3+ cationic complex 41d

[141] (22060(6) and 22017(6) pm)

respectively The silicon cobalt double bond (Si=CoV) distance (21848(8) pm) in

cobalt(V) complex 41e[144]

is also longer than dative SirarrCoI bond lengths in complex

41 Structures of cited compounds are drawn for clarity in Scheme 338


- 82 -

Scheme 338 Structural features of 41 and cited silylene cobalt complexes

Figure 325 Molecular structures of 41 (top) and 42 (bottom) Thermal ellipsoids

are drawn at 30 probability level Hydrogen atoms and solvent molecules are

omitted for clarity Selected bond lengths (pm) and angles (deg) for 41 (top) Co1-Si1

21252(14) Co1-Si2 21200(14) Si1-C6 1894(5) Si2-C11 1887(5) Si1-N1

1898(4) Si1-N2 1907(4) Si2-N3 1904(4) Si2-N4 1922(4) Si1-Co1-Si2

9389(5) N1-Si1-N2 6847(15) N3-Si2-N4 6866(16) C6-Si1-Co1 13254(14)

for 42 (bottom) Co1-Ge1 21967(6) Co1-Ge2 21979(6) Ge1-C6 1965(4) Ge2-


- 83 -

C11 1961(4) Ge1-N1 2020(3) Ge1-N2 2031(3) Ge2-N3 2041(3) Ge2-N4

2029(3) Ge1-Co1-Ge2 9279(2) N1-Ge1-N2 6490(11) N3-Ge2-N4 6485(11)

C6-Ge1-Co1 13280(10) C11-Ge2-Co1 13140(10)

The Co-Ge bonds of 42 (21967(6) and 21979(6) pm) are also shorter than those in

the germylene cobalt(0) complex [((Me3Si)2N)2GerarrCo(CO)3]2[145]

(2262(1) pm) and

the tetragermacyclobutadiene-CoICp complex η

4-((

tBu2MeSi)4Ge4)CoCp (24616(3)

and 25036(3) pm)[90d]

respectively In fact the Co-Ge bonds in 42 are the shortest

Co-Ge bonds known to date The relatively short EII-Co bonds in 41 and 42 suggest

that 38 and 40 are two of the strongest σ-donor ligands in the series of divalent silicon

and germanium compounds as yet

373 Formation of bis-silylene 38 bridged complex 44 and 45

To test σ-donor ability of bis-(silylene) 38 versus carbonyl a ligand exchange

reaction between 38 and (CO)2CoCp[146]

was explored When 38 was allowed to react

with two molar equivalents of (CO)2CoCp the bis-silylene 41 bridged bimetallic

cobalt complex 44[33a]

could be obtained in 87 yield accompanied by half CO-

elimination of (CO)2CoCp (Scheme 339) The reaction of bis-silylene 38 with one

molar equivalent of (CO)2CoCp furnished the same product but the isolable yield was

low The structure of 44 was determined by multinuclear NMR spectroscopy

elemental analysis and infrared spectroscopy

Scheme 339 Synthesis of bis-silylene 38 bridged CoI(CO)Cp complex 44


- 84 -

The 1H-NMR spectrum of complex 44 exhibits a singlet for four

tBu groups at δ =

124 ppm A singlet (δ = 523 ppm) and two sets of hyperfine coupled triplet (δ = 461

and 476 ppm) are assigned to protons of CoICp group and ferrocene with the ratio of

1044 The resonance of phenyl protons appears in aromatic resonance region The

29Si-NMR spectrum of 44 shows a singlet resonance at δ = 857 ppm similar to that

of 41 In the 13

C-NMR spectrum of 44 one characteristic signal for the CO ligands

appears at δ = 2078 ppm Furthermore the IR spectrum of 44 exhibits a strong

stretching band at ν = 1888 cmminus1

attributed to the carbonyl groups on the CoI atoms

The observed CO stretching frequency of 44 is much lower than those of 41a

(ν = 1968 cmminus1

)[141]

thus indicating that the bis-silylene substituted ferrocene 38 is a

much stronger σ-donor than chlorosilylene 26[32b]

Another carbonyl-silylene exchange reaction was investigated between bis-

silylene 38 and diiron nonacarbonyl Fe2(CO)9 Toluene was added to a 11 mixture of

38 and Fe2(CO)9 at room temperature to afford a bis-silylene 38 bridged Fe(CO)4

complex 45 in 73 yield (Scheme 340) The structure of 45 was determined by

multinuclear NMR spectroscopy infrared spectroscopy and elemental analysis

Scheme 340 Synthesis of bis-silylene 38 bridged Fe(CO)4 complex 45

The 1H-NMR spectrum of complex 45 shows a singlet for four

tBu groups at δ =

109 ppm Two singlets at δ = 483 and 500 ppm are assigned to protons of ferrocene

Multiplets in the range of 699-739 ppm are resonances of phenyl protons The 29

Si-

NMR spectrum of 45 exhibits a singlet resonance at δ = 1050 ppm It is much more


- 85 -

downfield shifted than those in complexes 41 (820 ppm) and 44 (857 ppm) One

characteristic strong signal for the CO ligands appears at δ = 2169 ppm in the 13

C-

NMR spectrum of 45 It is compatible to the resonance (δ = 2167 ppm) of the

silylene-Fe(CO)4 complex aL(

tBuO)SirarrFe(CO)4

[71] In the IR spectrum of 45 the

CO stretching frequencies (2026 1948 1900 cmminusl

) are also quite uniform to those of

this complex (2026 1949 1899 cmminusl

)[71]

Due to the rotation energy of ferrocene and

the symmetric bulky coordination of Fe the second CO-substitution could be more

difficult Consequently a chelated complex 38rarrFe(CO)3 was not observed during the

isolation of products

38 Application of Ni Co complexes as precatalysts

The investigation of the catalytic activity of complexes 28 41 and 42 was carried

out in collaboration with Stephan Enthaler (TU Berlin)[33a]

Nickel or palladium catalyzed cross-coupling reactions between organozinc halides

and aromatic halides constitute an excellent synthetic method for polyfunctional

aromatic compounds[147]

To probe the catalytic activity of bis-silylene oxide Ni0

complex 28 a cross-coupling reaction between benzyl zinc chloride and p-methoxyl-

iodobenzene was investigated (Scheme 341) The direct iodine substitution of p-

methoxyl-iodobenzene with organometallic compounds was not expected without a

catalyst In the presence of Ni0 complex 28 as precatalyst the C(sp

2)-C(sp

3) coupling

reaction was observed and product 46 was obtained in 65 yield indicating a

potential application for this kind of complexes


- 86 -

Scheme 341 Application of 28 as precatalyst in cross-coupling reactions

Moreover the reactivity of the resulting complexes 41 and 42 as precatalysts for

Co-mediated [2+2+2] cycloaddition reactions of phenylacetylene and acetonitrile was

expected[148]

It is known numerous cobalt complexes have been successfully applied

as precatalysts in [2+2+2] cycloaddition reactions and this becomes a powerful tool in

organic chemistry to form arene and heteroarene moieties[148-149]

Thus the catalytic

abilities of complexes 41 and 42 in [2+2+2] cycloaddition reactions were investigated

(Scheme 342)

Scheme 342 Application of 41 and 42 as precatalyst in [2+2+2] cycloaddition reactions

A first set of experiments was dedicated to the benchmark trimerization of phenyl

acetylene which resulted in the quantitative formation of isomers 47a and 47b in the

presence of complex 41 To our surprise similar attempts to employ 42 as precatalyst

failed with no product formation presumably due to a stronger coordination of GeII

atoms to the Co center which consequently prevents from the formation of an active


- 87 -

site for substrate coordination In another set of experiments the formation of

substituted pyridines 48a and 48b by [2+2+2] cycloaddition of phenyl acetylene and

an excess of acetonitrile was detected[150]

The catalytic activity of SiII-Co complex 41

was exhibited distinctly again while no product formation could be observed with

GeII-Co complex 42 To some extent the application of CpCo(CO)2 as precatalyst

gave however substituted pyridines in lower yield (48a (3) and 48b (11))[33a]

Scheme 343 Proposed mechanism of 41 as precatalyst for the [2+2+2] cycloaddition

A possible mechanism for the [2+2+2] cycloaddition of phenylacetylene or nitrile

to obtain 47 and 48 is proposed[149a]

as depicted in Scheme 343 At first bis-silylene

complex 41 could participate in a ligand substitution reaction with the


- 88 -

phenylacetylene to form an acetylene side-on complex Co-I The latter undergoes a

ring-formation to give the σ-bonded CoIII

complex Co-II which is saturated in

coordination with bis-silylene 38 Then intermediate Co-III is formed after π-donor

substitution by acetylene The succedent ring-enlargement furnishes the transient σ-

complex Co-IV and a subsequent elimination of products 47 and 48 occurs leading to

the active species Co-I by coordination of two phenylacetylene molecules In this

cobalt catalyzed transformation bis-silylene 38 serves as an important accessorial

ligand making the Co-center with high electron density more active and stabilizing the

intermediates Co-II and Co-IV

Unexpectedly complex 41 is catalytically active while complex 42 is inactive The

possible reason for this could be a stronger coordination of the GeII donor centers to

Co which hampers the creation of an active site at CoI for the substrate coordination

Summary

- 89 -

4 SUMMARY AND CONCLUSION

In this work various new metallylenes of Si Ge and Sn and bis-metallylenes

(interconnected and spacer separated) were synthesized The properties and

coordination ability of new metallylenes toward transition-metals including Fe Co

Ni and Pd were studied

The reduction of chlorogermylene (nacnac)GeCl 1[80]

with excess of elemental

potassium furnished the first potassium germylene anionic salt 3[83]

in 33 yield

along with the β-diketiminato germylene amide 4[83]

(nacnac)Ge-NH-Dip in 31

yield 3 consists of a dimeric half-sandwich complex interconnected via

intermolecular GerarrK dative bonds Each half-sandwich moiety consists of a

K(OEt2)2 cation which is η5-coordinated to the anionic five-membered planar GeNC3

ring with a considerable Cpmacr-like aromatic stabilization This is supported by density

functional theory (DFT) calculations The treatment of (nacnac)GeCl3 2[82]

with KC8

gave the same products 3 4 and novel Ge4-cluster compound 5[83]

in very low yield

Compound 5 represents a dipotassium salt of the first ldquoheavyrdquo cyclobutadiene-like

dianion (CBD2-

) consisting of a planar Ge42minus

core

Summary

- 90 -

Figure 41 Central molecular structures of 3 (left) and 5 (right)

The reactivity of compound 3 as nucleophile towards chlorogermylene 1[80]

and

chlorostannylene 7[80]

was examined Coupling reactions of 3 with 1 or 7 led to the

corresponding bis-germylene 6[104]

in 66 yield and germylene-stannylene 8[104]

in

34 yield respectively Compounds 6 and 8 were fully characterized including by X-

ray diffraction analysis The new compound 6 represent the first asymmetric

substituted bis-germylene with the shortest GeI-Ge

I bond length The germylene-

stannylene 8 is the first example with a GeI-Sn

I coupling as yet This novel structural

feature was explained with asymmetric structure and some ionic charge distribution

between 5- and six-membered rings by DFT calculation


Summary

- 91 -

The synthesis of new ligands 12 or 20[110]

was easily accessible from lithium amide

10 with corresponding benzimidoyl chloride 11 or 19[112]

by salt metathesis reactions

Subsequent reactions of 12 with nBuLi and then with GeCl2middotdioxane furnished


in 82 yield Germylene 16[110]

was obtained by

dehydrochloration of 14 with carbene 15[113]

in 78 yield The molecule of

zwitterionic germylene 16 bears two reactivity positions a strong nucleophilic

methylene group and a nucleophilic(s-orbital)-electrophilic(p-orbital) germylene site

Thus treatment of 16 with ammonia gas or with water resulted in the formation of

corresponding aminogermylene 17[110]

or germylene hydroxide 18[110]

in high yield

The reaction of compound 20 with nBuLi and then with GeCl2sdotdioxane led to the

unusual oxo-chloro-germylene 22 in 80 yield Dichlorogermane 23 was obtained by

reaction of 21 with GeCl4 through dehydrochloration with carbene 15 as a base in

57 yield All new compounds have been characterized spectroscopically and

crystallographically 12 and 20 are new types of asymmetric β-diketiminato ligands

with a fused six-membered C6-ring to prevent the transformation of ligand backbone

and side-reactions of ligands They are promising ancillary chelating ligand for the

synthesis of novel silylenes and stannylenes The preparation of new germylenes

added significantly to the growing field of GeII-chemistry capable of small molecule

activation

Summary

- 92 -

Figure 43 Molecular structures of 16 (left) and 18 (right)


A new challenge in metallylene synthetic chemistry is the preparation of chalcogen

(O S Se) bridged bis-metallylene species Here the synthesis and isolation of the

oxygen bridged bis-silylene 28[32a]

was achieved for the first time Reaction of

(HSiCl2)2O with lithium amidinate gave disiloxane 27[32a]

in 53 yield The bis-

silylene oxide 28 was available by dehydrochloration of 27 employing LiN(SiMe3)2 in

76 yield The molecule of 28 contains two triply coordinated Si atoms and two lone

pairs one at each of the Si centers The Si1-O-Si2 angle of 28 is slightly bent and

DFT calculations revealed that the Si1-O-Si2 angle deformation energy is very small

Compound 28 with one molar equiv of Ni(cod)2 furnished the Ni0 complex 29

[32a]

in 91 yield which is the first bidentate bis-silylene transition-metal complex with

18 valence electrons at the metal-site In diamagnetic complex 29 the two silylene

Summary

- 93 -

subunits and the two ethylenes of the COD-ligand are tetrahedrally coordinated to the

Ni0 atom The strong σ-donor character of 28 led to a more electron-rich Ni center

This work will lead to new insights into the chelating silylene ligand transition-metal

coordination chemistry


To possibly get access to a phosphasilyne a desilylation reaction that is phosphino

silylene 30[128]

was allowed to react with Ph3PCl2 30 was synthesized by facile

phosphanylation of chlorosilylene 26 with LiP(SiMe3)2 in 83 yield Surprisingly the

reaction of 30 with one molar equiv of Ph3PCl2 led to the formation of the unique

product 31[128]

as yellow crystals in 72 yield

An X-ray crystal structure analysis confirmed that 31 is a dimer of the desired

phosphasilyne Compound 31 is the first 4π-elektron Si2P2-cycloheterobutadiene

derivate with two-coordinated P atoms and a planar Si2P2-ring The Si-P bond lengths

in 31 represent intermediate values between the Si=P bond length and the Si-P bond

length The equal Si-P distances in 31 already indicate σ- and π-electron resonance

stabilization within the Si2P2 cycle which has been confirmed by theoretical

calculations According to DFT investigation each Si atom in the Si2P2-ring bears a

large positive net charge (+1204) while the P atoms in the ring have somewhat

Summary

- 94 -

smaller negative charges (-0765)

Figure 46 Molecular structure of 31

Pincer arenes having divalent heavier group 14 elements are currently

unprecedented in synthetic chemistry but assumed to form complexes that could

serve as precatalysts for various organic transformations due to their coordination

ability towards metals Here the synthesis of the first bis-silylene-based SiCSi pincer

arene ligand 35[33b]

through the substitution of chlorosilylene 26[32b]

by 13-dilithium

resorcinolate 34 could be achieved in 79 yield Treatment of 35 with Pd(PPh3)4

afforded the unexpected silylene-silyl(phenyl)-palladium(II) complex 36[33b]

as orange

crystals in 81 yield

In compound 36 the PdII atom adopts a typical distorted square-planar

configuration defined by the carbon atom C1 two silylene SiII atoms and the silyl

SiIV

atom which is bonded with a hydrogen atom because of hydride shift to Si1 after

C-H activation by Pd Owing to the coordinative saturation of the Pd center one

silylene subunit (Si4) remains ldquofreerdquo With the help of theoretical investigation the

Summary

- 95 -

reaction mechanism was explained and the exothermic transformation from 35 to 36

was confirmed This is a new approach in metallylene transition-metal coordination

chemistry with complexes being potentially applicable in catalytic transformation

Figure 47 Molecular structure of 36 tBu and phenyl groups are not shown

Also a type of bis-metallylene with a ferrocendiyl spacer for new bidentate σ-donor

properties was investigated Here the facile synthesis of the first bis(silylenyl)- and

bis(germylenyl)-substituted ferrocenes 38 and 40 as well as their corresponding CoI

complexes could be described for the first time By salt metathesis reaction of 11rsquo-

dilithioferrocene 37 with chlorosilylene 26[32b]

or chlorogermylene 39[41]

furnished

bis-silylene 38[33a]

in 70 yield or bis-germylene 40[33a]

in 77 yield respectively

Reactions of a suitable CoICp precursor with bis-silylene 38 afforded the bis-silylene

CoI complex 41

[33a] in 30 yield Likewise the bis-germylene Co

I complex 42

[33a]

could be synthesized from 40 with CoICp fragment and isolated in 61 yield

Summary

- 96 -


Figure 49 Molecular structures of 41 (left) and 42 (right) tBu and phenyl groups

are not shown

Compounds 38 and 40 represent the first examples of isolable ferrocene bridged

bis-silylene or bis-germylene respectively The isolated products 41 and 42 are the

first heterobimetallic complexes of CoICp with bis-silylene or bis-germylene

functioning in a chelating fashion In both complexes cobalt is coordinated on one

side by cyclopentadienyl and on another side by bis-silylene 38 or bis-germylene 40

and contains 18 valence electrons The Co-Si bonds in 41 and the Co-Ge bonds in 42

belong to the shortest Co-E (E = Si Ge) bonds known to date The relatively short EII-

Co bonds in 41 and 42 indicate that 38 and 40 are two of the strongest σ-donor ligands

in the series of divalent silicon and germanium compounds as yet due to the electron-

rich ferrocene and metallylene segments

In addition in the presence of Ni0 complex 28 as precatalyst the C(sp

2)-C(sp

3)

cross-coupling[147]

reaction between benzyl zinc chloride and p-methoxyl-iodo-

benzene was observed evidently The catalytic abilities of complexes 41 and 42 in Co-

Summary

- 97 -

mediated [2+2+2] cycloaddition reactions of phenylacetylene and acetonitrile were

probed[148-150]

However complex 41 is catalytically active while complex 42 is

inactive The possible reason for this could be a stronger coordination of the GeII

donor centers to Co which hampers the creation of an active site at CoI for the

substrate coordination

Experimental section

- 98 -

5 EXPERIMENTAL SECTION

51 General section

All experiment and manipulations were carried out under dry oxygen-free nitrogen

using standard Schlenk techniques or in an inert atmosphere of purified nitrogen The

glassware used in all manipulations was dried at 150 degC prior to use cooled to

ambient temperature under high vacuum and flushed with N2 The handling of solid

samples and the preparation of samples for spectroscopic measurements were carried

out inside a glove-box where the O2 and H2O levels were normally kept below 1 ppm

All solvents were purified using conventional procedures and freshly distilled under

N2 atmosphere prior to use They were stored in Schlenk-vessels containing activated

molsieves Benzene toluene n-pentane and n-hexane were purified by distillation

from Nabenzophenone Et2O and THF were initially pre-dried over KOH and then

distilled from Nabenzophenone CH2Cl2 and chloroform were dried by stirring over

CaH2 at ambient temperature

For transfer of solvents or solutions stainless steel cannulas were used which were

stored in the oven at 120 degC The transfer was enabled by the vessel of origin being

left under a positive pressure of protective gas and the receptacle vessel of closed

with a pressure release value By filtration stainless steel cannula containing a filter-

head at one end was utilized Whatman (GFB 25) filters were affixed to the filter end

of the cannula with Teflon tape After use cannulas were cleaned immediately by

thorough rinsing with acetone followed by dilute HCl water acetone and

dichloromethane

In the case of low temperature reactions Dewar vessels were filled with acetone

and dry-ice was added until reaching the desired temperature Ethanol liquid

nitrogen was also employed for reactions in needs of -90 degC


- 99 -

52 Analytical methods

NMR Measurements NMR samples of air andor moisture sensitive compounds were

all prepared under inert atmosphere The deuterated solvents were dried by stirring

over Na (C6D6 THF-d8) or CaH2 (CDCl3) distilled under N2 atmosphere and stored in

Schlenk-vessels containing activated molsieves The 1H- and

13C-NMR spectra were

recorded on ARX 200 (1H 200 MHz

13C 50 MHz) and ARX 400 (

1H 400 MHz

13C

10046 MHz) spectrometers from the Bruker Company The 29

Si-NMR spectra were

recorded only on ARX 400 (29

Si 7949 MHz) spectrometer

The 1H and

13C

1H NMR spectra were calibrated against the residual proton and

natural abundance 13

C resonances of the deuterated solvent relative to

tetramethylsilane (benzene-d6 δH 715 ppm and δC 1280 ppm chloroform-d1 δH 727

ppm and δC 770 ppm THF-d8 δH 173 ppm and δC 253 ppm Heteronuclear spectra

were calibrated as follows 31

P1H external 85 H3PO4

119Sn

1H external SnMe4

Whereby in each case an 1-mm glass capillary tube containing the standard substance

was placed in the appropriate solvent in a 5 mm NMR tube and the spectrum recorded

The abbreviations used to denote the multiplicity of the signals are as follows s =

singlet d = doublet t = triplet q = quartet sept = septet m = multiplet br = broad

Infra-red spectroscopy IR spectra (4000 ndash 400 cm-1

) were recorded on a Perkin-Elmer

Spectra 100 FT-IR spectrometer bands were reported in wave-numbers (cm-1

)

Samples of solids were measured as KBr pellets Air or moisture sensitive samples

were prepared in the glove-box and measured immediately The spectra were

processed using the program OMNIC and the abbreviations associated with the

absorptions quoted are vs = very strong s = strong m = medium w = weak br =

broad the intensities of which were assigned on the basis of visual inspection

UV-vis Spectrometry UV-vis spectrophotometric investigations were carried out on a

Specord S 600 spectrophotometer from Analytik Jena AG Pure samples of the

investigated substance were dissolved in dry solvents at suitable concentration The

UV-vis cuvette was filled and closed in a Schlenk tube under N2 atmosphere

Mass Spectrometry Mass spectra were performed at the Chemistry institute of


- 100 -

Technical University Berlin EI spectra were recorded on a 311A Arian MATAMD

spectrometer ESI mass spectra were recorded on a Thermo Scientific Orbitrap LTQ

XL spectrometer Solid samples were prepared in glove box and the solution of

samples was prepared 15 min before the measurement under N2 atmosphere Mass

spectra are presented in the standard form mz (percent intensity relative to the base

peak)

Elemental analysis The C H N and S analyses of all compounds were carried out on

a Thermo Finnigan Flash EA 1112 Series instrument Air or moisture sensitive

samples were prepared in ldquotin-boatsrdquo in the glove box Samples with halogen were

filled in the ldquosilver-boatsrdquo for better measuring accuracy

Melting Point determinations A BSGT Apotec II instrument was used for the

determination of melting points Samples were prepared in glass capillary tubes under

N2 atmosphere The melting point was determined while the melded examples had the

same color like the solid before Without melting of samples the color change was

observed was determined as decomposition temperature

Single crystal X-ray structure determinations Crystals suitable to the single crystal

x-ray structure analysis were put on a glass capillary with perfluorinated oil and

measured in a cold nitrogen stream The data of all measurements were collected with

an Oxford Diffraction Xcalibur S Saphire diffractometer at 150 K (MoKα radiation λ

= 071073 Aring) The structures were solved by direct methods Refinements were

carried out with the SHELXL-97[151]

software package All thermal displacement

parameters were refined anisotropically for non-H atoms and isotropically for H

atoms All refinements were made by full matrix least-square on F2 In all cases the

graphical representation of the molecular structures was carried out using Ortep32

version 108 The details for the individual structure solutions included in this

dissertation are available in the appendix


- 101 -

53 Starting Materials

Commercially available starting materials were used as received The following

important precursors were prepared according to literature procedures The references

are shown in Table 51

Table 51 Starting materials and references

Compound References Compound References

GeCl2dioxane [27] 15 (HCNtBu)2C [113]

(HSiCl2)2O [117] 19 Ph(Cl)C=N-iPr [112]

1 (nacnac)GeCl [80] 24 tBuN=C=N

tBu [152]

2 (nacnac)GeCl3 [82] 26 aLSiCl [32b]

7 (nacnac)SnCl [80] 32 (Me3Si)2N-SnCl [53]

9 (C5H10)C=N-Dip [111] 39 aLGeCl [41]

11 Ph(Cl)C=N-Dip [112]


- 102 -

54 Synthesis and characterization of new compounds

521 The first germylene anion 3 and the germylene 4

To a solution of 1[80]

(133 g 253 mmol) in THF (15 mL) was added potassium

(148 g 379 mmol) at room temperature After stirring for 4 h the color of the

solution changed from yellow to brown Volatiles were removed under reduced

pressure and the residue was first extracted with hexane (60 mL in portions) and then

with diethyl ether (60 mL in portions)

The combined diethyl ether extract was filtrated and the filtrate was concentrated

and stored at -20degC for 5 d yielding the first germylene anion 3 as pale yellow crystals

(030 g 083 mmol 33)

C25H44GeKNO2 MW 50236

Properties soluble in THF slightly soluble in Et2O spontaneous

combustion towards air

Melting Point 220 degC (decomp)

1H NMR (40013 MHz THF-D8 298K) δ = 108 (d

3JHH = 7 Hz 6 H

CHMe2) 112 (d 3JHH = 7 Hz 6 H CHMe2) 184 (s 3 H

NCMe) 262 (s 3 H GeCMe) 298 (sept 3JHH = 7 Hz 2 H

CHMe2) 618 (s 1 H γ-CH) 691- 698 (m 3 H arom H)

13C

1H NMR (10061 MHz THF-D8 298K) δ = 182 (NCMe) 203

(GeCMe) 238 (CHMe2) 269 (CHMe2) 280 (CHMe2) 1185

(γ-C) 1224-1745 (arom C GeCMe NCMe)

Elemental analysis calcd () for C17H24GeKN(C4H10O)022 C 5797 H 713 N

378 Found C 5764 H 694 N 367

The combined hexane extract was filtered and the filtrate was concentrated and

stored at -20 degC for 2 d yielding the new germylene 4 as yellow crystals (052 g 078


- 103 -

mmol 31)

NHN

GeN

Dip

DipDip

C41H59GeN3 MW 66657

Properties soluble in hexane sensitive towards air

Melting Point 192 - 193 degC

1H NMR (40013 MHz C6D6 298K) δ = 091 (d

3JHH = 68 Hz 6 H

CHMe2) 109 (d 3JHH = 68 Hz 6 H CHMe2) 114 (d

3JHH =

68 Hz 6 H CHMe2) 122 (m br 12 H CHMe2) 130 (d

3JHH = 68 Hz 6 H CHMe2) 162 (s 6 H NCMe) 329-340

(m 6 H CHMe2) 503 (s 1 H γ-CH) 564 (s 1 H NH) 683

ndash 718 (m 9 H arom H)

13C

1H NMR (10061 MHz C6D6 298K) δ = 225 (CHMe) 234 (NCMe)

240 (br CHMe) 245 (CHMe) 247 (CHMe) 256 (CHMe)

288 (CHMe) 292 (CHMe) 964 (γ-C) 1171 ndash 1635 (arom

C NCMe)

EI-MS mz () 6674 (03 [M]+) 4912 (100 [M -

iPr2C6H3NH]

+)

Elemental analysis calcd () for C41H59GeN3 C 7388 H 892 N 630 Found

C 7354 H 868 N 613

522 Alternative preparation of 3 4 and synthesis of compound 5

To a precooled (-78 degC) solution of 2[82]

(097 g 16 mmol) in THF (15 mL) was

added KC8 (094 g 69 mmol) After stirring for 4 h the reaction mixture was allowed

to warm to room temperature and the color of the solution changed from yellow to

brown The reaction mixture was allowed to stir an additional 48 h at room

temperature The signal of compound 1[80]

also disappeared in the 1H-NMR spectrum

of the resulting mixture and compound 3 and 4 were observed as main products

Volatiles were removed under reduced pressure and the residue was first extracted

with hexane (50 mL in portions) and then with diethyl ether (50 mL in portions)

The combined diethyl ether extract was filtered the filtrate was concentrated to 10


- 104 -

mL and stored at -20degC for 48 h yielding 3 as pale yellow crystals (024 g 067 mmol

42) The combined hexane extract was concentrated and stored at -20degC for 24 h

yielding 4 as yellow crystals (042 g 063 mmol 39)

Further concentration of the supernate and cooling at -20degC for 48 h yielded 5 as red

crystals along with colorless crystals of the known β-diketiminato potassium complex

C66H100Ge4K2N4O2 MW 135028

Elemental analysis calcd () for C66H100Ge4K2N4O2 C 7890 H 1003 N 278

Found C 7821 H 999 N 281

523 The asymmetric bis-germylene 6

C46H65Ge2N3 MW 80531

To a solution of the germylene anion 3 (138 mg 0263 mmol) in THF (10 mL) at -

30 degC was added the solution of the chlorogermylene 1[80]

(93 mg 0263 mmol) in

THF (10 mL) The color of the solution changed from yellow to dark red After

stirring for further 2 h at room temperature volatiles were removed under reduced

pressure and the residue was extracted with hexane (30 mL) The filtrate was

concentrated and stored at -30degC for 5 days yielding 6 as dark red crystals (140 mg

017 mmol 66)

Properties soluble in hexane very sensitive towards air

Melting Point gt169 degC (decomp)


- 105 -

1H NMR (40013 MHz C6D6 298K) δ = 107 (d

3JHH = 7 Hz 12 H


3JHH = 7

Hz 6 H CHMe2) 124 (d 3JHH = 7 Hz 6 H CHMe2) 161 (s

6 H NCMe) 202 (s 3 H NCMe) 262 (s 3 H GeCMe) 301

(sept 3JHH = 7 Hz 2 H CHMe2) 319 (sept

3JHH = 7 Hz 2 H

CHMe2) 367 (sept 3JHH = 7 Hz 2 H CHMe2) 518 (s 1 H 6-

ring-γ-CH) 682 (s 1 H 5-ring-β-CH) 702- 718 (m 9 H

arom H)

13C

1H NMR (10061 MHz C6D6 298K) δ = 191 (5-ring-NCMe) 210

(GeCMe) 240 (6-ring-NCMe) 248 (CHMe2) 249 (CHMe2)

250 (CHMe2) 258 (CHMe2) 259 (CHMe2) 261 (CHMe2)

279 (CHMe2) 288 (CHMe2) 289 (CHMe2) 1028 (6-ring-γ-

C) 1238 (5-ring-β-C) 1240 ndash 1694 (arom C GeCMe

NCMe)

UV-vis λ [nm] = 315 (intense) 358 (intense) 502 (2600)

EI-MS mz () 491 (45 [M-(C3NGe) ring fragment]+) 316 (15 [M-

(C3N2Ge) ring fragment]+)

Elemental analysis calcd () for C46H65Ge2N3 C 6861 H 814 N 522 Found

C 6884 H 800 N 516

524 The first germylene-stannylene 8

C46H65GeN3Sn MW 85138

To a suspension of germylene anion 3 (116 mg 0328 mmol) in Et2O (15 mL) at -

70 degC was added the solution of 7[80]

(187 mg 0328 mmol) in Et2O (15 mL) The

color of the solution changed from yellow to dark red After stirring for further 2 h at

room temperature the volatiles of the reaction mixture were removed under reduced



- 106 -

concentrated and stored at -30degC for 10 days yielding 8 as dark red-black solid (96 mg

011 mmol 34) The solid was solved in Et2O and stored at 0 degC for 24 h building

dark red crystals



1H NMR (40013 MHz C6D6 298K) δ = 085 (d

3JHH = 7 Hz 6 H


3JHH = 7

Hz 6 H CHMe2) 121 (d 3JHH = 7 Hz 6 H CHMe2) 127 (d

3JHH = 7 Hz 6 H CHMe2) 129 (d

3JHH = 7 Hz 6 H CHMe2)

165 (s 6 H SnNCMe) 227 (s 3 H GeNCMe) 300 (s 3 H

GeCMe) 305 (sept 3JHH = 7 Hz 2 H CHMe2) 333 (sept

3JHH

= 7 Hz 2 H CHMe2) 378 (sept 3JHH = 7 Hz 2 H CHMe2)

510 (s 1 H 6-ring-γ-CH) 691 (s 1 H 5-ring-β-CH) 705-

721 (m 9 H arom H)

13C






NCMe)

119Sn NMR

(C6D6) δ = -197

UV-vis λ [nm] = 314 (15000) 363 (14500) 541 (2800)


(C3N2Sn) ring fragment]+)

Elemental analysis calcd () for C46H65GeN3Sn C 6489 H 770 N 494

Found C 6444 H 764 N 477


- 107 -

525 The novel β-diketiminato-type ligand 12

C37H48N2 MW 52079


(200 g 777 mmol) in 200 mL Et2O at -78 degC was added 16

M nBuLi (486 mL 777 mmol) in hexane and the reaction mixture was stirred at

room temperature overnight resulting in slightly yellow slurry The reaction mixture

was cooled to -78 degC again and the solution of 11[112]

(210 g 700 mmol) in Et2O

(100 mL) was added The reaction mixture was stirred at room temperature for 2 h

and then refluxed for 1 h Water free Et3NHCl (108 g 777 mmol) was added to the

reaction mixture and stirred All solvents were evaporated in vacuo The residue was

extracted with warm hexane and crystallized at -30 degC to obtain 229 g (440 mmol

63 ) of the novel β-diketiminato-type ligand 12 as colorless crystals

Properties soluble in hexane DCM and Ethanol stable towards air

Melting Point 148 ~ 150 degC

1H NMR (40013 MHz CDCl3 298K) δ = 117 (d

3JHH = 7 Hz 6 H


3JHH = 7

Hz 6 H CHMe2) 134 (d 3JHH = 7 Hz 6 H CHMe2) 164 (m

4 H Cy-CH2) 187 (s 1 H NH) 217 (m 4 H Cy-CH2) 335

(m 4 H CHMe2) 696 (s 3 H arom H) 715- 727 (m 8 H

arom H)

13C

1H NMR (10061 MHz CDCl3 298K) δ = 218 (Cy-CH2) 221

(CHMe2) 236 (CHMe2) 238 (Cy-CH2) 247 (CHMe2) 256

(CHMe2) 280 (CHMe2) 282 (CHMe2) 285 (Cy-CH2) 286

(Cy-CH2) 977 (Cy-CCN) 1222-1441 (arom C) 1600 (Cy-

CN) 1658 (Ph-CN)

ESI-MS mz calcd for C37H49N2+ 5213896 Found 5213878

Elemental analysis calcd () for C37H48N2 C 8533 H 929 N 538 Found C

8518 H 927 N 547


- 108 -

526 The new chlorogermylene 14

N

N

Ph

Dip

Dip

Cl

Ge

C37H47ClGeN2 MW 62788

nBuLi (881 mL 141 mmol 16 M) was added to a solution of 12 (720 g 138

mmol) in 80 mL of Et2O at -78 degC The solution was allowed slowly to warm to room

temperature and stirred for 4 h GeCl2middotdioxane[27]

(330 g 142 mmol) was added to

the reaction solution at -78 degC The resulting suspension was stirred overnight at room

temperature Volatiles were removed under reduced pressure and the residue was

extracted with warm toluene two times The filtrate was concentrated and stored at -

30 degC yielding 14 as yellow crystals (710 g 113 mmol 82 )

Properties soluble in hexane toluene sensitive towards air

Melting Point 203 degC

1H NMR (40013 MHz C6D6 298K) δ = 097 (d

3JHH = 7 Hz 3 H


3JHH = 7

Hz 3 H CHMe2) 121-127 (m 9 H CHMe2) 128-139 (m

4 H Cy-CH2) 144 (d 3JHH = 7 Hz 3 H CHMe2) 155 (d

3JHH = 7 Hz 3 H CHMe2) 203-227 (m 4 H Cy-CH2) 317


3JHH = 7 Hz 1 H

CHMe2) 394 (sept 3JHH = 7 Hz 1 H CHMe2) 417 (sept

3JHH = 7 Hz 1 H CHMe2) 680- 739 (m 11 H arom H)

13C

1H NMR (10061 MHz C6D6 298K) δ = 213 (CHMe2) 226 (CHMe2)

231 (Cy-CH2) 239 (CHMe2) 245 (CHMe2) 246 (Cy-CH2)



295 (Cy-CH2) 315 (Cy-CH2) 1089 (Cy-CCN) 1234-1476

(arom C) 1651 (Cy-CN) 1688 (Ph-CN)

ESI-MS mz calcd for C37H47ClGeN2+ 6282640 Found 6282639

Elemental analysis calcd () for C37H47ClGeN2 C 7078 H 754 N 446

Found C 7073 H 762 N 457


- 109 -

527 The new germylene 16

C37H46GeN2 MW 59142

Germylene chloride 14 (300 g 479 mmol) and 13-Bis-tert-butyl- imidazol-2-

ylidene 15[113]

(091 g 502 mmol) were dissolved in toluene (25 mL) at room

temperature and stirred for 48 h resulting in a white precipitate of the corresponding

NHCmiddotHCl salt The color of the solution changed from yellow to brown-red The

solvent was removed under reduced pressure and the residue was extracted with warm

hexane two times The combined filtrate was concentrated and stored at -30 degC

yielding 16 as red crystals (220 g 373 mmol 78 )



1H NMR (40013 MHz C6D6 298K) δ = 115 (d

3JHH = 7 Hz 6 H


3JHH = 7

Hz 12 H CHMe2) 155 (m 2 H Cy-CH2) 204 (m 2 H Cy-

CH2) 221 (m 2 H Cy-CH2) 369 (sept 3JHH = 7 Hz 2 H

CHMe2) 380 (sept 3JHH = 7 Hz 2 H CHMe2) 415 (t

3JHH =

44 Hz 1 H C=CH) 675- 725 (m 11 H arom H)

13C

1H NMR (10061 MHz C6D6 298K) δ = 226 (CHMe2) 234 (Cy-CH2)

247 (CHMe2) 258 (Cy-CH2) 259 (CHMe2) 273 (CHMe2)

283 (CHMe2) 284 (CHMe2) 315 (Cy-CH2) 987 (Cy-CH)

1117 (Cy-CCN) 1236-1431 (arom C) 1473 1474 (Cy-CN

Ph-CN)

IR (KBr cm-1

) 704 (s) 787 (s) 939 (m) 1104 (s) 1135 (s) 1204 (s) 1248 (s)

1296 (s) 1322 (s) 1365 (s) 1439 (s) 1461 (s) 1535 (m) 1600

(s) 2822 (m) 2865 (s) 2922 (s) 2957 (w) 3022 (w) 3061 (m)

ESI-MS mz calcd for C37H47GeN2+ 5932951 Found 5932950


C 7495 H 800 N 484


- 110 -

528 Aminogermylene 17

C37H49GeN3 MW 60845

A red solution of 16 (591 mg 100 mmol) in toluene (15 mL) was exposed to dry

ammonia gas for 10 min at room temperature The solution turned to a yellow color

and was stirred for 6 h at ambient temperature The solvent was removed and the

residue was dissolved in hexane (40 mL) The concentrated solution was stored at 0

degC yielding 17 as yellow crystals (560 mg 092 mmol 92 )



1H NMR (40013 MHz C6D6 298K) δ = 106 (d

3JHH = 7 Hz 3 H

CHMe2) 117 (d 3JHH = 7 Hz 3 H CHMe2) 120-136 (m 15

H CHMe2 4 H Cy-CH2) 142 (d 3JHH = 7 Hz 3 H CHMe2)

154 (s 2 H NH2) 200-213 (m 4 H Cy-CH2) 346 (sept

3JHH = 7 Hz 1 H CHMe2) 357 (sept

3JHH = 7 Hz 1 H



13C


234 (CHMe2) 237 (Cy-CH2) 244 (CHMe2) 246 (Cy-CH2)



293 (Cy-CH2) 315 (Cy-CH2) 1023 (Cy-CCN) 1234-1462

(arom C) 1643 (Cy-CN) 1669 (Ph-CN)

IR (KBr cm-1

) 561 (s) 704 (s) 752 (s) 796 (s) 839 (m) 922 (s) 1096 (s)

1143 (s) 1174 (s) 1252 (s) 1304 (s) 1360 (s) 1430 (s) 1543

(s) 2865 (m) 2961 (s) 3021 (w) 3048 (m) 3343 (w) 3430

(w)


C 7272 H 810 N 683


- 111 -

529 Germylene hydroxide 18

C37H48GeN2O MW 60943

A diluted solution of H2O in THF (179 mL 100 mmol 056 M) was dropped into

a solution of 16 (591 mg 100 mmol) in toluene (10 mL) at -30 degC The solution

turned to a yellow color and was stirred for 6 h at ambient temperature The solvents

were removed and the residue was redissolved in hexane (40 mL) The concentrated

solution was stored at 0 degC yielding 18 as yellow crystals (580 mg 095 mmol 95 )



1H NMR (40013 MHz C6D6 298K) δ = 111 (d

3JHH = 7 Hz 3 H



166 (s 1 H OH) 195-221 (m 4 H Cy-CH2) 335 (sept


3JHH = 7 Hz 1 H



13C





291 (Cy-CH2) 314 (Cy-CH2) 1028 (Cy-CCN) 1233-1464

(arom C) 1647 (Cy-CN) 1666 (Ph-CN)

IR(KBr cm-1

) 561 (s) 713 (s) 743 (s) 770 (s) 791 (s) 839 (s) 926 (m)

1056 (m) 1104 (s) 1148 (s) 1170 (s) 1257 (s) 1313 (s) 1339

(s) 1365 (s) 1430 (s) 1470 (s) 1539 (s) 2861 (s) 2961 (s)

3018 (w) 3057 (m) 3643 (m)

ESI-MS mz calcd for C37H47GeN2O+ 6092900 Found 6092901

Elemental analysis calcd () for C37H48GeN2O C 7292 H 794 N 460


- 112 -

Found C 7300 H 786 N 464


C28H38N2 MW 40230

At -78 degC to a solution of 9[111]

(150 g 583 mmol) in 150 mL Et2O was added 16






and then refluxed for 1 h All solvents were evaporated in vacuo The residue was


60 ) of 20 as colorless blocks



1H NMR (40013 MHz CDCl3 298K) δ = 109 (d

3JHH = 7 Hz 6 H


3JHH = 7



CHMe2) 323 (m 1 H CHMe2) 713- 753 (m 8 H arom H)

1203 (d 3JHH = 7 Hz 1 H NH)

13C


(CHMe2) 238 (Cy-CH2) 244 (CHMe2) 246 (CHMe2) 276

(Cy-CH2) 280 (CHMe2) 300 (Cy-CH2) 459 (CHMe2) 977

(Cy-CCN) 1226 1228 1275 1282 1284 1371 1389

1453 (arom C) 1576 (Cy-CN) 1673 (PhCN)



- 113 -


8270 H 977 N 679

5211 Oxo-chlorogermylene 22

C28H37ClGeN2O MW 52570


mmol) in 15 mL Et2O at -78 degC The solution was allowed to slowly warm to room





extracted with warm toluene The filtrate was concentrated and stored at -30 degC

yielding 22 as yellow crystals (105 g 200 mmol 80 )



1H NMR (40013 MHz C6D6 298K) δ = 106 (d

3JHH = 7 Hz 3 H


3JHH = 7

Hz 3 H CHMe2) 121 (m 2 H Cy-CH2) 127 (d 3JHH = 7



1 H Cy-CH2) 202 (m 1 H Cy-CH2) 206 (m 2 H Cy-CH2)

284 (sept 3JHH = 7 Hz 1 H CHMe2) 367 (sept

3JHH = 7 Hz

1 H CHMe2) 396 (sept 3JHH = 7 Hz 1 H CHMe2) 688 (m

1 H arom H) 705-724 (m 7 H arom H)

13C


231 (Cy-CH2) 240 (CHMe2) 241 (CHMe2) 253 (CHMe2)



- 114 -

293 (Cy-CH2) 312 (Cy-CH2) 537 (CHMe2) 1068 (Cy-

CCN) 1239 1250 1267 1271 1288 1294 1388 1410

1446 1469 (arom C) 1620 (Cy-CN) 1654 (Ph-CN)

Elemental analysis calcd () for C28H37ClGeN2O C 6397 H 709 N 533

Found C 6426 H 725 N 551

5212 β-Diketiminato germanium dichloride 23

C28H36Cl2GeN2 MW 54415

nBuLi (32 mL 512 mmol 16 M) was added to a solution of 20 (201 g 500 mmol)

in 30 mL of toluene at -78 degC The solution was allowed to warm to room temperature

and stirred for 4 h To this solution GeCl4 (107 g 500 mmol) and 13-Bis-tert-

butylimidazol-2-ylidene 15 (091 g 502 mmol) were added at -78 degC The resulting

suspension was stirred overnight at room temperature Volatiles were removed under

reduced pressure and the residue was extracted with warm hexane two times The

filtrate was concentrated and stored at -30 degC yielding 23 as yellow crystals (156 g

287 mmol 57 )

Properties soluble in hexane sensitive towards wet air


1H NMR (40013 MHz C6D6 298K) δ = 113 (d

3JHH = 7 Hz 6 H


3JHH = 7




3JHH =

42 Hz 1 H C=CH) 701-726 (m 8 H arom H)

13C

1H NMR (10061 MHz C6D6 298K) δ = 237 (CHMe2) 243 (Cy-

CH2) 247 (CHMe2) 254 (Cy-CH2) 257 (CHMe2) 286


- 115 -

(CHMe2) 304 (Cy-CH2) 511 (CHMe2) 1036 (Cy-CH)

1125 (Cy-CCN) 1248 1287 1296 1354 1391 1411

1421 1490 (arom C) 1682 (Cy-CN) 1709 (Ph-CN)

Elemental analysis calcd () for C28H36Cl2GeN2 C 6180 H 515 N 667

Found C 6203 H 517 N 679

5213 Amidinato disiloxane 27

C30H48Cl2N4OSi2 MW 60781

To a solution of tBuN=C=N

tBu

[152] (329 g 213 mmol) in Et2O (80 mL) PhLi (119

mL 214 mmol 18 M) was added at -78 degC The solution was raised to room

temperature and stirred for 2 h To this solution at -90 degC 1133-

tetrachlorodisiloxane[117]

(230 g 1065 mmol) was added in one minute The

resulting suspension was stirred overnight at room temperature Volatiles were

removed under reduced pressure and the residue was extracted with toluene (60 mL)

by 80 degC two times The filtrate was concentrated and stored at 0 degC for 24 h yielding

27 as colorless crystals (343 g 564 mmol 53)

Properties soluble in toluene sensitive towards wet air


1H NMR (40013 MHz CDCl3 298K) δ = 120 (s 36 H CMe3) 598

(s 2 H SiHCl) 733- 746 (m 10 H arom H)

13C

1H NMR (10061 MHz CDCl3 298K) δ = 317 (CMe3) 544 (CMe3)

1276 1285 1297 1337 (arom C) 1711 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = -1110

IR(KBr cm-1

) 606 (s) 658 (m) 711 (s) 733 (s) 760 (s) 789 (s) 934 (s)

1068 (s) 1200 (s) 1269 (s) 1378 (s) 1486 (s) 1550 (s) 1566

(s) 1612 (s) 1783 (w) 1826 (w) 1950 (w) 1969 (w) 2000


- 116 -

(w) 2135 (s) 2188 (s) 2909 (s) 2934 (s) 2971 (s) 3232 (m)

ESI-MS mz calcd for C30H49Cl2N4OSi2+ 6072822 Found 6072844

Elemental analysis calcd () for C30H48Cl2N4OSi2 C 5928 H 796 N 922

Found C 5971 H 797 N 913

5214 Bis-silylene oxide 28

C30H46N4OSi2 MW 53488

Toluene (120 mL) was added to a mixture of 27 (260 g 428 mmol) and

LiN(SiMe3)2 (144 g 856 mmol) at ambient temperature After 2 h the solution turned

to an orange color with the formation of LiCl The resulting mixture was stirred

overnight The solvent was then removed and the residue was extracted with toluene

(100 mL) The filtrate was concentrated and stored at 0 degC for 24 h to yield yellow

crystals of 28 (175 g 327 mmol 76)

Properties slightly soluble in hexane very sensitive towards air


1H NMR (40013 MHz C6D6 298K) δ = 135 (s 36 H CMe3) 692-

731(m 10 H arom H)

13C

1H NMR (10061 MHz C6D6 298K) δ = 321 (CMe3) 530 (CMe3)

1277 1291 1299 1349 (arom C) 1623 (NCN)

29Si

1H NMR (7949 MHz C6D6 298K) δ = -161

IR(KBr cm-1

) 608 (s) 709 (s) 746 (s) 790 (s) 892 (m) 972 (s) 1032 (m)

1070 (m) 1208 (s) 1268 (m) 1359 (s) 1412 (s) 1446 (s)

1476 (s) 1577 (m) 1648 (m) 1778 (w) 1826 (w) 1899 (w)

1970 (w) 2248 (w) 2867 (s) 2902 (s) 2928 (s) 2964 (s)

3065 (m)


- 117 -

ESI-MS mz calcd 5353288 Found 5353227

Elemental analysis calcd () for C30H46N4OSi2 C 6736 H 867 N 1047

Found C 6688 H 857 N 1046

5215 Bis-silylene oxide nickel complex 29

C38H58N4NiOSi2 MW 70176

Toluene (20 mL) was added to a mixture of 28 (267 mg 050 mmol) and Ni(cod)2

(1375 mg 050 mmol) at ambient temperature The solution turned to a low-red color

and was stirred for 24 h The solvent was removed and the residue was extracted with

toluene (30 mL) The filtrate was concentrated to yield low-red crystals of 29 (319 mg

046 mmol 91) The remaining solid was crystallized from hexane at -30 degC

suitable for single crystal measurement


Melting Point gt 183 degC (decomp)

1H NMR (40013 MHz C6D6 298K) δ = 130 (s 36 H CMe3) 281

(m 4 H CH2) 295 (m 4 H CH2) 504 (s 4 H =CH) 686-

707 (m 10 H arom H)

13C

1H NMR (10061 MHz C6D6 298K) δ = 321 (CMe3) 337 (CH2) 535

(CMe3) 760 (=CH) 1277 1293 1296 1335 (arom C)

1690 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = 328

IR(KBr cm-1

) 607 (s) 644 (s) 698 (s) 750 (s) 792 (s) 925 (m) 1021 (m)

1075 (s) 1209 (s) 1267 (s) 1320 (m) 1361 (s) 1407 (s)

1444 (s) 1475 (s) 1578 (m) 1647 (m) 1775 (w) 1823 (w)


- 118 -

1902 (w) 1962 (w) 2280 (w) 2791 (s) 2855 (s) 2913 (s)

2975 (s) 3023 (m) 3063 (w)

ESI-MS mz () calcd 7003503 Found 7003577

Elemental analysis calcd () for C38H58N4NiOSi2 C 6504 H 833 N 798

Found C 6387 H 837 N 805

5216 Bis(trimethylsilyl)phosphino silylene 30

C21H41N2PSi3 MW 43679

Toluene (20 mL) was added to a mixture of chlorosilylene 26[32b]

(302 mg 102

mmol) and lithium bis(trimethylsilyl)phosphate (285 mg 103 mmol) at ambient

temperature The solution turned to a yellow color and was stirred for 3 h The solvent

was removed and the residue was extracted with hexane (30 mL) The filtrate was

concentrated and stored at -30 degC for 24 h yielding 30 as yellow crystals (371 mg

085 mmol 83)


Melting Point 149-150 degC

1H NMR (40013 MHz C6D6 298K) δ = 058 (d

3JP-H = 44 Hz 18 H

SiMe3) 124 (s 18 H CMe3) 681-699 (m 2 H arom H)

734-741 (m 3 H arom H)

13C

1H NMR (10061 MHz C6D6 298K) δ = 44 (d

3JC-P = 100 Hz

SiMe3) 315 (d 4JC-P = 16 Hz CMe3) 540 (CMe3) 1289

1292 1293 1344 (arom C) 1572 (d 3JC-P = 95 Hz

NCN)

29Si

1H NMR (7949 MHz C6D6 298K) δ = 31 (d

1JSi-P = 229 Hz

PSiMe3) 440 (d 1JSi-P = 1943 Hz N2SiP)

31P NMR (81012 MHz C6D6 298K) δ = - 2110


- 119 -

ESI-MS mz () calcd for C21H41N2PSi3 4362315 Found 4362524

5217 24-Disila-13-diphosphacyclobutadiene 31

C30H46N4P2Si2 MW 58083

Toluene (20 mL) was added to a mixture of 30 (309 mg 071 mmol) and

triphenylphosphine dichloride (237 mg 071 mmol) at room temperature The

solution was stirred for 24 h The solvent was removed and the residue was extracted

with THF (30 mL) The filtrate was concentrated to yield yellow crystals of 31 (148

mg 025 mmol 72)

Properties soluble in THF sensitive towards air


1H NMR (40013 MHz THF-D8 298K) δ = 135 (s 36 H CMe3) 705-

733 (m 10 H arom H)

13C

1H NMR (10061 MHz THF-D8 298K) δ = 331 (CMe3) 534

(CMe3) 1256 1276 1294 1359 (arom C) 1710 (NCN)

29Si

1H NMR (7949 MHz THF-D8 298K) δ = 267 (t

1JSi-P = 998 Hz)

31P NMR (81012 MHz THF-D8 298K) δ = - 1649

ESI-MS mz () calcd for C30H46N4P2Si2 5802736 Found

5802361


- 120 -

5218 Aminosilylene-stannylene dichloride 33

C21H41Cl2N3Si3Sn MW 60944


(336 mg 114

mmol) and Chloro-amino-stannylene 32[53]

(360 mg 114 mmol) at room temperature

The solution was stirred for 24 h The solvent was removed and the residue was

extracted with hexane (20 mL) The filtrate was concentrated to yield colorless

crystals of 33 (343 mg 056 mmol 49)

Properties soluble in hexane very sensitive towards air decomposed

slowly at room temperature

Melting Point gt 25 degC (slowly decomp)

Elemental analysis mz () calcd for C21H41Cl2N3Si3Sn C 4139 H 678 N

689 Found C 4195 H 701 N 706

5219 46-Di-tert-butylresorcinyl bis-silylene 35

C44H66N4O2Si2 MW 73919

At -78 degC to a solution of 46-Di-tert-butylresorcinol (150 g 675 mmol) in 30 mL

Et2O was added 16 M nBuLi (85 mL 136 mmol) in hexane and the reaction

mixture was stirred at room temperature for 4 h resulting in white slurry The reaction

mixture was cooled to -78 degC again and added the solution of chlorosilylene 26[32b]

(398 g 135 mmol) in 50 mL toluene After the addition the mixture was stirred at

room temperature overnight All solvents were evaporated in vacuo The residue was

extracted with the warm hexane and crystallized at -30 degC 395 g bis-silylene 35 (534


- 121 -

mmol 79 ) as slightly yellow solid



1H NMR (40013 MHz C6D6 298K) δ = 124 (s 36 H NC(CH3)3)

174 (s 18 H ArC(CH3)3) 693 - 713 (m 8 H arom H) 754

(s 1 H Ar-H) 787 (s 1 H Ar-H) 802 (m 2 H arom H)

13C

1H NMR (10061 MHz C6D6 298K) δ = 309 (ArC(CH3)3) 318

(NC(CH3)3) 350 (ArC(CH3)3) 530 (NC(CH3)3) 1096

1243 1276 1295 1297 1313 1341 1552 (arom C)

1636 (NCN)

29Si

1H NMR (7949 MHz C6D6 298K) δ = -240

Elemental analysis mz () calcd for C44H66N4O2Si2 C 7049 H 900 N 758

Found C 7075 H 930 N 756

5220 SiCSi palladium complex 36

C88H132N8O4PdSi4 MW 158480

Bis-silylene 35 (600 mg 081 mmol) and Pd(PPh3)4 (468 mg 041 mmol) were

mixed in 25 mL hexane at room temperature and stirred for 24 h The hexane solution

was filtrated and the white precipitate was washed with 10 mL hexane one time The

solid product was dried under reduced pressure to yield 520 mg (033 mmol 81 )

white powders The product was dissolved in warm hexane and stored at room

temperature for 10 days giving some orange crystals of 36 The reaction of bis-


- 122 -

silylene 35 with one molar equiv of Pd(PPh3)4 in toluene furnishes the same product

but the isolable yield is only about 30

Properties slightly soluble in hexane sensitive towards air


1H NMR (40013 MHz C6D6 298K) δ = 105 (s 9 H C(CH3)3) 108

(s 9 H C(CH3)3) 114 (s 9 H C(CH3)3) 116 (s 9 H

C(CH3)3) 131 (s 9 H C(CH3)3) 139 (s 9 H C(CH3)3)155

(s 9 H C(CH3)3) 168 (s 9 H C(CH3)3) 177 (s 9 H

C(CH3)3) 180 (s 9 H C(CH3)3) 185 (s 9 H C(CH3)3) 212

(s 9 H C(CH3)3) 659 (s 1 H SiH) 686- 789 (m 22 H

arom H) 816 (s 1 H Ar-H)

13C

1H NMR (10061 MHz C6D6 298K) δ = 309 (C(CH3)3) 311

(C(CH3)3) 314 (C(CH3)3) 316 (C(CH3)3) 318 (C(CH3)3)

319 (C(CH3)3) 320 (C(CH3)3) 322 (C(CH3)3) 328

(C(CH3)3) 332 (C(CH3)3) 333 (C(CH3)3) 343 (C(CH3)3)

349 350 351 357 526 527 537 539 540 541 542

561 1112 1225 1236 1243 1256 1258 1271 1285

1287 1289 1291 1293 1294 1302 1303 1318 1323

1324 1326 1340 1342 1378 1380 1381 1409 1430

1533 1559 1585 1613 1622 1654 1731 1742

29Si

1H NMR (7949 MHz C6D6 298K) δ = -87 (LSi) 397 (Si-H) 623

658 (LSiPd)

IR(KBr cm-1

) 623 (m) 706 (m) 764 (m) 860 (m) 1056 (m) 1108 (m) 1206

(m) 1272 (m) 1365 (m) 1418 (s) 1446 (m) 1476 (m) 1446

(m) 1476 (m) 1495 (m) 1591 (m) 2135 (w) 2875(m) 2906

(s) 2964 (s) 3061 (w)

Elemental analysis mz () calcd for C88H132N8O4PdSi4 C 6669 H 840 N

707 Found C 6616 H 875 N 676


- 123 -

5221 Bis(silylenyl)-ferrocene 38

C40H54FeN4Si2 MW 70290

16 M nBuLi (423 ml 677 mmol) was added to a hexane (10 mL) solution of

ferrocene (600 mg 323 mmol) and TMEDA (937 mg 806 mmol) at 0 degC The

reaction mixture was stirred at 50 degC for 4 h The reaction mixture was cooled to -78

degC A toluene (30 mL) solution of chlorosilylene 26[32b]

(190 g 645 mmol) was

added dropwise to the reaction mixture over 5 min After stirring at room temperature

overnight all volatiles were removed in vacuo and the residue was extracted with

pentane Compound 38 was obtained as deep red crystals in 70 yield (159 g 226

mmol) on storage of a saturated pentane solution at 0 degC

Properties soluble in hexane spontaneous combustion towards air



451 (t 3JHH = 15 Hz 4 H FeCH) 472 (t

3JHH = 15 Hz 4 H

FeCH) 692- 707 (m 10 H arom H)

13C

1H NMR (10061 MHz C6D6 298K) δ = 318 (NC(CH3)3) 530

(NC(CH3)3) 709 (FeCH) 727 (FeCH) 846 (SiC) 1289

1294 1305 1349 (arom C) 1604 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = 433

ESI-MS mz () calcd for [M++1] 703331 Found 703329

Elemental analysis calcd () for C40H54FeN4Si2 C 6835 H 774 N 797

Found C 6803 H 767 N 778


- 124 -

5222 Bis(germylenyl)-ferrocene 40

C40H54FeGe2N4 MW 79201




degC A toluene (25 mL) solution of chlorogermylene 39[41]




warm hexane Compound 40 was obtained as orange crystals in 77 yield (163 g

206 mmol) on storage of a saturated hexane solution at 0 degC



1H NMR (40013 MHz C6D6 298K) δ = 111 (s 36 H NC(CH3)3) 461

(t 3JHH = 16 Hz 4 H FeCH) 471 (t

3JHH = 16 Hz 4 H

FeCH) 691- 697 (m 6 H arom H) 712- 717 (m 4 H arom

H)

13C


(NC(CH3)3) 701 (FeCH) 723 (FeCH) 920 (GeC) 1289

1290 1302 1369 (arom C) 1659 (NCN)

Elemental analysis calcd () for C40H54FeGe2N4 C 6666 H 687 N 707 Found

C 6655 H 701 N 707


- 125 -

5223 Bis(silylenyl)-ferrocene CoICp complex 41

tBu

N

N

tBu

PhSi

tBu

N

N

tBu

Ph Si

Co

Fe

C45H59CoFeN4Si2 MW 82693

In a glove box CoBr2 (202 mg 092 mmol) NaCp (81 mg 092 mmol) and KC8

(131 mg 097 mmol) were weighed into a Schlenk flask TolueneTHF solvent

mixture (41 15 mL) was added to the mixture and the solution was stirred for 18 h at

room temperature The bis-silylene 38 (650 mg 092 mmol) was added to the solution

and the mixture was stirred for 5 h at room temperature All volatiles were evaporated

in vacuo and the residue was extracted with warm hexane Compound 41 was

obtained as deep red crystals in 30 yield (230 mg 028 mmol) on storage of a

saturated hexane solution at room temperature




440 (t 3JHH = 16 Hz 4 H FeCH) 461 (t

3JHH = 16 Hz 4 H

FeCH) 496 (s 5 H CoCH) 680- 684 (m 2 H arom H)

692- 696 (m 6 H arom H) 720- 723 (m 2 H arom H)

13C


(NC(CH3)3) 700 (FeCH) 745 (FeCH) 780 (CoCH) 851

(SiC) 1291 1297 1300 1343 (arom C) 1673 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = 820


Elemental analysis calcd () for C45H59CoFeN4Si2 C 6536 H 719 N 678

Found C 6612 H 724 N 686


- 126 -

5224 Bis(germylenyl)-ferrocene CoICp complex 42

tBu

N

N

tBu

PhGe

tBu

N

N

tBu

Ph Ge

Co

Fe

C45H59CoFeGe2N4 MW 91604

In a glove box CoBr2 (83 mg 038 mmol) NaCp (33 mg 038 mmol) and KC8 (54

mg 040 mmol) were weighed into a Schlenk flask TolueneTHF solvent mixture

(41 15 mL) was added to the mixture and the solution was stirred for 18 h at room

temperature The bis-germylene 40 (300 mg 038 mmol) was added to the solution








438 (t 3JHH = 15 Hz 4 H FeCH) 459 (t

3JHH = 15 Hz 4 H

FeCH) 504 (s br 5 H CoCH) 684- 688 (m 2 H arom H)

695- 698 (m 6 H arom H) 714- 718 (m 2 H arom H)

13C



(GeC) 1287 1296 1300 1361(arom C) 1680 (NCN)

Elemental analysis calcd () for C45H59CoFe Ge2N4 C 5900 H 649 N 612

Found C 5942 H 664 N 590


- 127 -

5225 Bis(silylenyl)-ferrocene carbonyl CoICp complex 44

C52H64Co2FeN4O2Si2 MW 100697

To a solution of ferrocenyl bis-silylene 39 (250 mg 036 mmol) in 10 ml hexane

was added a solution of CpCo(CO)2 (130 mg 072 mmol) in 8 ml hexane The

reaction mixture was stirred for 5 h at room temperature All solvents were evaporated

in vacuo The corresponding bis-silylene cobalt(I) complex 44 was isolated as brown

air- and moisture-sensitive solids in 87 yield (310 mg 031 mmol)

Properties soluble in toluene spontaneous combustion towards air



461 (m 4 H FeCH) 476 (m 4 H FeCH) 523 (s 10 H

CoCH) 683- 695 (m 6 H arom H) 702- 706 (m 2 H

arom H) 745- 748 (m 2 H arom H)

13C



(CoCH) 1287 1296 1300 1324 (arom C) 1687 (NCN)

2078 (br CO)

29Si

1H NMR (7949 MHz C6D6 298K) δ = 857

IR(KBr cm-1

) 500 (m) 539 (w) 564 (m) 628 (s) 703 (m) 757 (s) 792 (m)

825 (w) 1028 (m) 1081 (w) 1146 (m) 1199 (s) 1275 (m)

1360 (m) 1388 (m) 1417 (s) 1438 (w) 1474 (m) 1520 (s)

1641 (s) 1888 (s) 2869 (s) 2901 (m) 2926 (m) 2965 (s)

1520 (s) 3097 (w)

Elemental analysis mz () calcd for C52H64Co2FeN4O2Si2 C 6202 H 641 N


- 128 -

556 Found C 6287 H 630 N 571

5226 Bis(silylenyl)-ferrocene Fe(CO)4 complex 45

C48H54Fe3N4O8Si2 MW 103867

Toluene (15 mL) was added to a mixture of ferrocenyl bis-silylene 39 (500 mg

071 mmol) and Fe2(CO)9 (259 mg 071 mmol) at room temperature The solution

was stirred for 12 h The solvent was evaporated in vacuo The corresponding bis-

silylene iron(0) complex 45 was isolated as yellow-brown air- and moisture-sensitive

solids in 73 yield (540 mg 052 mmol)




(s 4 H FeCH) 500 (s 4 H FeCH) 699- 712 (m 8 H arom

H) 736- 739 (m 2 H arom H)

13C



1287 1303 1308 (arom C) 1704 (NCN) 2169 (CO)

29Si

1H NMR (7949 MHz C6D6 298K) δ = 1050

IR(KBr cm-1

) 630 (s) 765 (w) 1028 (m) 1035 (m) 1200 (m) 1370 (w)

1400 (m) 1474 (w) 1609 (w) 1648 (w) 1900 (s) 1948 (s)

1996(w) 2026 (s) 2865 (w) 2930 (m) 2965 (m)

Elemental analysis mz () calcd for C48H54Fe3N4O8Si2 C 5550 H 524 N

539 Found C 5623 H 517 N 566

References

- 129 -

6 REFERENCES

1 P Pyykko Chem Rev 1988 88 563

2 N V Sidgwick Clarendon Oxford 1950 1 287 (b) R S Drago J Phys Chem 1958 62

353

3 P P Power Chem Rev 1999 99 3463 (b) R C Fischer P P Power Chem Rev 2010 110

3877

4 R Janoschek Chemie in unserer Zeit 1988 22 128

5 (a) F S Kipping L L Lloyd Dalton Trans 1901 79 449 (b) N N Greenwood A

Earnshaw Chemistry of the Elements (2nd ed) 1997 362

6 (a) L Roumlsch P John R Reitmeier Silicon Compounds Organic In Ullmanns Encyclopedia

of Industrial Chemistry Wiley-VCH Verlag GmbH amp Co KGaA 2000 (b) A J O Lenick

Basic Silicone Chemistry ndash A Review 1999

7 S Yao Y Xiong M Brym M Driess J Am Chem Soc 2007 129 7268

8 Y Xiong S Yao M Driess J Am Chem Soc 2009 131 7562

9 Y Xiong S Yao R Muumlller M Kaupp M Driess Nature Chem 2010 2 577

10 (a) S Yao M Brym C Van Wuumlllen M Driess Angew Chem Int Ed 2007 46 4159 (b) S

Yao Y Xiong C Milsmann E Bill S Pfirrmann C Limberg M Driess Chem Eur J

2010 16 436

11 (a) K S Pitzer J Am Chem Soc 1948 70 2140 (b) R S Mulliken J Am Chem Soc

1955 77 884

12 (a) M Asay C Jones M Driess Chem Rev 2011 111 354 (b) S Yao Y Xiong M Driess

Organometallics 2011 30 1748 (c) Y Mizuhata T Sasamori N Tokitoh Chem Rev 2009

109 3479 (d) P P Power Organometallics 2007 26 4362 (e) P P Power Chem Rev 2003

103 789 (f) S Nagendran H W Roesky Organometallics 2008 27 457

13 (a) R West M J Fink J Michl Science 1981 214 1343 (b) M J Fink M J Michalczyk

K J Haller R West J Michl Chem Commun 1983 1010 (c) S Masamune Y Hanzawa

D J Williams J Am Chem Soc 1982 104 6136 (d) D E Goldberg D H Harris M F

Lappert K M Thomas Chem Commun 1976 261 (e) K W Klinkhammer T F Faumlssler H

Gruumltzmacher Angew Chem Int Ed 1998 37 124 (f) J T Snow S Murakami S

Masamune D J Williams Tetrahedron Lett 1984 25 4191 (g) M Weidenbruch Angew

Chem Int Ed 2003 42 2222

14 L Pauling J Am Chem Soc 1931 53 1367

15 (a) G Trinquier J P Malrieu P Riviere J Am Chem Soc 1982 104 4529 (b) J P

Malrieu G Trinquier J Am Chem Soc 1989 111 5916 (c) H Jacobsen T Ziegler J Am

Chem Soc 1994 116 3667

16 L Pu B Twamley P P Power J Am Chem Soc 2000 122 3524

17 M Kaupp P V R Schleyer J Am Chem Soc 1993 115 1061

18 A D Phillips R J Wright M M Olmstead P P Power J Am Chem Soc 2002 124 5930

19 N Takagi S Nagase Organometallics 2001 20 5498

20 M Stender A D Phillips R J Wright P P Power Angew Chem Int Ed 2002 41 1785

21 T L Allen W H Fink P P Power Dalton Trans 2000 407

References

- 130 -

22 A Sekiguchi R Kinjo M Ichinohe Science 2004 305 1755

23 D Bourissou O Guerret F P Gabbai G Bertrand Chem Rev 2000 100 39

24 M Denk R Lennon R Hayashi R West A V Belyakov H P Verne A Haaland M

Wagner N Metzler J Am Chem Soc 1994 116 2691

25 M Driess S Yao M Brym C V Wuellen Angew Chem Int Ed 2006 45 6730

26 M Kira S Ishida T Iwamoto C Kabuto J Am Chem Soc 1999 121 9722

27 V Lemierre A Chrostowska A Dargelos P Baylegravere W J Leigh C R Harrington Appl

Organom Chem 2004 18 676

28 R S Ghadwal H W Roesky S Merkel J Henn D Stalke Angew Chem Int Ed 2009 48

5683

29 L Jafarpour E D Stevens S P Nolan J Organomet Chem 2000 606 49

30 M Driess S Yao M Brym C Van Wuumlllen D Lentz J Am Chem Soc 2006 128 9628

31 (a) C-W So H W Roesky J Magull R B Oswald Angew Chem Int Ed 2006 45 3948

(b) C-W So H W Roesky P M Gurubasavaraj R B Oswald M T Gamer P G Jones S

Blaurock J Am Chem Soc 2007 129 12049

32 (a) W Wang S Inoue S Yao M Driess J Am Chem Soc 2010 132 15890 (b) S S Sen

H W Roesky D Stern J Henn D Stalke J Am Chem Soc 2009 132 1123

33 (a) W Wang S Inoue S Enthaler M Driess Angew Chem Int Ed 2012 51 6167 (b) W

Wang S Inoue E Irran M Driess Angew Chem Int Ed 2012 51 3691 (c) R Azhakar R

S Ghadwal H W Roesky H Wolf D Stalke Organometallics 2012 31 4588 (d) S S

Sen J Hey R Herbst-Irmer H W Roesky D Stalke J Am Chem Soc 2011 133 12311

34 R C Fischer L Pu J C Fettinger M A Brynda P P Power J Am Chem Soc 2006 128

11366

35 Y Wang Y Xie P Wei R B King H F Schaefer P Von R Schleyer G H Robinson

Science 2008 321 1069

36 S S Sen S Khan S Nagendran H W Roesky Acc Chem Res 2012 45 578

37 S S Sen A Jana H W Roesky C Schulzke Angew Chem Int Ed 2009 48 8536

38 C Jones S J Bonyhady N Holzmann G Frenking A Stasch Inorg Chem 2011 50

12315

39 D Gau R Rodriguez T Kato N Saffon-Merceron A De Coacutezar F P Cossiacuteo A Baceiredo

Angew Chem Int Ed 2011 50 1092

40 S P Green C Jones P C Junk K-A Lippert A Stasch Chem Commun 2006 3978

41 S Nagendran S S Sen H W Roesky D Koley H GrubmuLler A Pal R Herbst-Irmer

Organometallics 2008 27 5459

42 W-P Leung W-K Chiu K-H Chong T C W Mak Chem Commun 2009 6822

43 (a) S P Green C Jones A Stasch Science 2007 318 1754 (b) S J Bonyhady S P Green

C Jones S Nembenna A Stasch Angew Chem Int Ed 2009 48 2973 (c) S J Bonyhady

C Jones S Nembenna A Stasch A J Edwards G J Mcintyre Chem Eur J 2010 16 938

44 A Sidiropoulos C Jones A Stasch S Klein G Frenking Angew Chem Int Ed 2009 48

9701

45 Y Peng R C Fischer W A Merrill J Fischer L Pu B D Ellis J C Fettinger R H

Herber P P Power Chemical Science 2010 1 461

46 R Jambor B Kašnaacute K N Kirschner M Schuumlrmann K Jurkschat Angew Chem Int Ed

References

- 131 -

2008 47 1650

47 (a) C D Schaeffer J J Zuckerman J Am Chem Soc 1974 96 7160 (b) M J S Gynane

D H Harris M F Lappert P P Power P Riviere M Riviere-Baudet Dalton Trans 1977

2004 (c) M F Lappert P P Power M J Slade L Hedberg K Hedberg V Schomaker

Chem Commun 1979 369 (d) T Fjeldberg H Hope M F Lappert P P Power A J

Thorne Chem Commun 1983 639 (e) M Veith M Jarczyk V Huch Chem Ber 1988

121 347

48 M Veith R Lisowsky Angew Chem Int Ed 1988 27 1087

49 P B Hitchcock M F Lappert A J Thorne Chem Commun 1990 1587

50 R A Bartlett P P Power J Am Chem Soc 1990 112 3660

51 J-T Ahlemann H W Roesky R Murugavel E Parisini M Noltemeyer H-G Schmidt O

Muumlller R Herbst-Irmer L N Markovskii Y G Shermilovich Chem Ber 1997 130 1113

52 R S Ghadwal H W Roesky K Proumlpper B Dittrich S Klein G Frenking Angew Chem

Int Ed 2011 50 5374

53 R W Chorley P B Hitchock B S Jolly M F Lappert G A Lawless Chem Commun

1991 1302

54 A G Avent C Drost B Gehrhus P B Hitchcock M F Lappert Z Anorg Allg Chem

2004 630 2090

55 M Veith A Rammo Z Anorg Allg Chem 2001 627 662

56 M Veith J Fischer T R Prout M Noetzel P Hobein V Huch Inorg Chem 1991 30

4130

57 H Braunschweig P B Hitchcock M F Lappert L J M Pierssens Angew Chem Int Ed

1994 33 1156

58 H Braunschweig C Drost P B Hitchcock M F Lappert L J M Pierssens Angew Chem

Int Ed 1997 36 261

59 R E Allan M A Beswick G R Coggan P R Raithby A E H Wheatley D S Wright

Inorg Chem 1997 36 5202

60 (a) C Stanciu S S Hino M Stender A F Richards M M Olmstead P P Power Inorg

Chem 2005 44 2774 (b) Y Peng B D Ellis X Wang P P Power J Am Chem Soc

2008 130 12268

61 B Gehrhus P B Hitchcock M F Lappert Z Anorg Allg Chem 2005 631 1383

62 C Cui M M Olmstead J C Fettinger G H Spikes P P Power J Am Chem Soc 2005

127 17530

63 X Wang C Ni Z Zhu J C Fettinger P P Power Inorg Chem 2009 48 2464

64 S S Sen D Kratzert D Stern H W Roesky D Stalke Inorg Chem 2010 49 5786

65 H-X Yeong H-W Xi K H Lim C-W So Chem Eur J 2010 16 12956

66 (a) F E Hahn A V Zabula T Pape A Hepp Eur J Inorg Chem 2007 2007 2405 (b) A

V Zabula F E Hahn T Pape A Hepp Organometallics 2007 26 1972 (c) A V Zabula T

Pape A Hepp F E Hahn Organometallics 2008 27 2756

67 S-H Zhang C-W So Organometallics 2011 30 2059

68 O T Summerscales M M Olmstead P P Power Organometallics 2011 30 3468

69 (a) M Veith W Frank Angew Chem 1985 97 213 (b) M Veith Angew Chem Int Ed

1987 26 1 (c) H Chen R A Bartlett H V R Dias M M Olmstead P P Power Inorg

References

- 132 -

Chem 1991 30 3390 (d) R E Allan M A Beswick A J Edwards M A Paver M-A

Rennie P R Raithby D S Wright Dalton Trans 1995 1991 (e) W J Grigsby T Hascall

J J Ellison M M Olmstead P P Power Inorg Chem 1996 35 3254 (f) R E Allan M A

Beswick M K Davies P R Raithby A Steiner D S Wright J Organomet Chem 1998

550 71 (g) M E G Mosquera J S Palmer A D Hopkins D S Wright Phosphorus

Sulfur Silicon Relat Elem 1999 150 107 (h) M Veith M Opsoumllder M Zimmer V Huch

Eur J Inorg Chem 2000 2000 1143 (i) D R Armstrong F Benevelli A D Bond N

Feeder E A Harron A D Hopkins M Mcpartlin D Moncrieff D Saacuteez E A Quadrelli

A D Woods D S Wright Inorg Chem 2002 41 1492 (j) T Chivers Timothy j Clark M

Krahn M Parvez G Schatte Eur J Inorg Chem 2003 2003 1857 (k) J F Eichler O Just

W S Rees Inorg Chem 2006 45 6706 (l) D J Eisler T Chivers Chem Eur J 2006 12

233 (m) H Vaňkaacutetovaacute L Broeckaert F De Proft R Olejniacutek J Turek Z Padělkovaacute A

Růžička Inorg Chem 2011 50 9454

70 (a) A Meltzer C Praumlsang M Driess J Am Chem Soc 2009 131 7232 (b) A Meltzer C

Praumlsang C Milsmann M Driess Angew Chem Int Ed 2009 48 3170 (c) H Ogino The

Chemical Record 2002 2 291 (d) S Inoue M Driess Angew Chem Int Ed 2011 50

5614 (e) M Stoelzel C Praumlsang S Inoue S Enthaler M Driess Angew Chem Int Ed

2012 51 399

71 W Yang H Fu H Wang M Chen Y Ding H W Roesky A Jana Inorg Chem 2009 48

5058

72 (a) J Choi A H R Macarthur M Brookhart A S Goldman Chem Rev 2011 111 1761

(b) N Selander K L N J Szaboacute Chem Rev 2011 111 2048 (c) M E Van Der Boom D

Milstein Chem Rev 2003 103 1759

73 W Tang X Zhang Chem Rev 2003 103 3029

74 (a) A P Shaw J R Norton D Buccella L A Sites S S Kleinbach D A Jarem K M

Bocage C Nataro Organometallics 2009 28 3804 (b) L-C Song J-T Liu Q-M Hu G-

F Wang P Zanello M Fontani Organometallics 2000 19 5342 (c) S Shekhar J F

Hartwig J Am Chem Soc 2004 126 13016

75 N A Marinos Modellsysteme fuumlr die [NiFe]-Hydrogenase und Zinkkatalysatoren fuumlr die

Hydrosilylierung Technischen Universitaumlt Berlin Germany 2011

76 (a) C M Jensen D Morales-Morales The Chemistry of Pincer Compounds Elsevier

Science Amsterdam 2007 (b) M Albrecht G Van Koten Angew Chem Int Ed 2001 40

3750 (c) M Albrecht M M Lindner Dalton Trans 2011 40 8733 (d) D Benito-Garagorri

K Kirchner Acc Chem Res 2008 41 201 (e) C Gunanathan D Milstein Acc Chem Res

2011 44 588

77 (a) N Selander K J Szabo Dalton Trans 2009 6267 (b) H Zhang A Lei Dalton Trans

2011 40 8745 (c) J Dupont C S Consorti J Spencer Chem Rev 2005 105 2527

78 Silyl-silylene transition-metal complexes see (a) K Ueno S Seki H Ogino Chem Lett

1993 22 2159 (b) H Tobita H Wada K Ueno H Ogino Organometallics 1994 13 2545

(c) K Ueno A Masuko H Ogino Organometallics 1997 16 5023 (d) H Wada H Tobita

H Ogino Organometallics 1997 16 3870 (e) H Tobita H Kurita H Ogino

Organometallics 1998 17 2844 (f) H Tobita H Kurita H Ogino Organometallics 1998

17 2850 (g) H Wada H Tobita H Ogino Chem Lett 1998 27 993 (h) K Ueno A

References

- 133 -

Masuko H Ogino Organometallics 1999 18 2694 (i) H Tobita T Sato M Okazaki H

Ogino J Organomet Chem 2000 611 314 (j) H Koshikawa M Okazaki S Matsumoto

K Ueno H Tobita H Ogino Chem Lett 2005 34 1412 (k) K Ueno S Ito K Endo H

Tobita S Inomata H Ogino Organometallics 1994 13 3309

79 For reviews on silylene complexes see (a) M S Eisen Transition-Metal Silyl Complexes

In The Chemistry of Organic Silicon Compounds John Wiley amp Sons Ltd 2003 pp 2037 (b)

M Okazaki H Tobita H Ogino Dalton Trans 2003 493 (c) R Waterman P G Hayes T

D Tilley Acc Chem Res 2007 40 712

80 Y Ding H W Roesky M Noltemeyer H G Schmidt P P Power Organometallics 2001

20 1190

81 L Bourget-Merle M F Lappert J R Severn Chem Rev 2002 102 3031

82 B Raumlke F Zuumllch Y Ding J Prust H W Roesky M Noltemeyer H G Schmidt Z Anorg

Allg Chem 2001 627 836

83 W Wang S Yao C Van WuLlen M Driess J Am Chem Soc 2008 130 9640

84 (a) R West H Sohn D R Powell T Muumlller Y Apeloig Angew Chem Int Ed 1996 35

1002 (b) W P Freeman T D Tilley L M Liable-Sands A L Rheingold J Am Chem

Soc 1996 118 10457

85 J Fischer J Baumgartner C Marschner Organometallics 2005 24 1263

86 M Stender A D Phillips P P Power Inorg Chem 2001 40 5314

87 M Driess S Yao M Brym C Van Wuumlllen Angew Chem Int Ed 2006 45 4349

88 W D Woodul A F Richards A Stasch M Driess C Jones Organometallics 2010 29

3655

89 W Clegg E K Cope A J Edwards F S Mair Inorg Chem 1998 37 2317

90 (a) K Takanashi V Y Lee M Matsuno M Ichinohe A Sekiguchi J Am Chem Soc 2005

127 5768 (b) K Takanashi V Y Lee M Ichinohe A Sekiguchi Angew Chem Int Ed

2006 45 3269 (c) K Takanashi V Y Lee M Ichinohe A Sekiguchi Eur J Inorg Chem

2007 2007 5471 (d) V Y Lee Y Ito H Yasuda K Takanashi A Sekiguchi J Am Chem

Soc 2011 133 5103

91 S P Mallela S Hill R A Geanangel Inorg Chem 1997 36 6247

92 P V R Schleyer C Maerker A Dransfeld H Jiao N J R V E Hommes J Am Chem

Soc 1996 118 6317

93 For a review see Z Chen C S Wannere C Corminboeuf R Puchta P V R Schleyer

Chem Rev 2005 105 3842

94 (a) R Ahlrichs M Baumlr M Haumlser H Horn C Koumllmel Chem Phys Lett 1989 162 165 (b)

M Haumlser R Ahlrichs J Comput Chem 1989 10 104

95 O Treutler R Ahlrichs J Chem Phys 1995 102 346

96 (a) A D Becke Phys Rev A 1988 38 3098 (b) J P Perdew Phys Rev B 1986 33 8822

97 (a) A Schaumlfer C Huber R Ahlrichs J Chem Phys 1994 100 5829 (b) K Eichkorn F

Weigend O Treutler R Ahlrichs Theor Chem Acc 1997 97 119

98 K Eichkorn O Treutler H Oumlhm M Haumlser R Ahlrichs Chem Phys Lett 1995 242 652

99 U Meier C Van Wuumlllen M Schindler J Comput Chem 1992 13 551

100 (a) C Van Wuumlllen Chem Phys Lett 1994 219 8 (b) C Van Wuumlllen Phys Chem Chem

Phys 2000 2 2137

References

- 134 -

101 (a) P J Stephens F J Devlin C F Chabalowski M J Frisch J Phys Chem 1994 98

11623 (b) A D Becke J Chem Phys 1993 98 1372 (c) C T Lee W T Yang R G Parr

Phys Rev 1988 37 785

102 W Kutzelnigg U Fleischer M Schindler NMR basis principles and progress Springer

Berlin 1990 Vol 23 page 169

103 (a) C Corminboeuf T Heine G Seifert P V R Schleyer J Weber Phys Chem Chem

Phys 2004 6 273 (b) P Von Rague Schleyer M Manoharan Z-X Wang B Kiran H Jiao

R Puchta N J R Van Eikema Hommes Org Lett 2001 3 2465

104 W Wang S Inoue S Yao M Driess Chem Commun 2009 2661

105 H Schaumlfer W Saak M Weidenbruch Organometallics 1999 18 3159

106 Y Sugiyama T Sasamori Y Hosoi Y Furukawa N Takagi S Nagase N Tokitoh J Am

Chem Soc 2006 128 1023

107 A Schaumlfer W Saak M Weidenbruch Organometallics 2003 22 215

108 (a) K H Pannell L Parkanyi H Sharma F Cervantes-Lee Inorg Chem 1992 31 522 (b)

A Kawachi Y Tanaka K Tamao J Organomet Chem 1999 590 15

109 Y Xiong S Yao M Driess Chem Asian J 2009 4 1323

110 W Wang S Inoue S Yao M Driess Organometallics 2011 30 6490

111 W Keim S Killat C F Nobile G P Suranna U Englert R Wang S Mecking L D

Schroumlder J Organomet Chem 2002 662 150

112 P H M Budzelaar A B Van Ort A G Orpen Eur J Inorg Chem 1998 1485

113 N M Scott R Dorta E D Stevens A Correa L Cavallo S P Nolan J Am Chem Soc

2005 127 3516

114 L W Pineda V Jancik H W Roesky D Neculai A M Neculai Angew Chem Int Ed

2004 43 1419

115 A Jana I Objartel H W Roesky D Stalke Inorg Chem 2009 48 798

116 S S Sen G Tavcar H W Roesky D Kratzert J Hey D Stalke Organometallics 2010 29

2343

117 R West J Am Chem Soc 1953 75 1002

118 R Drake I Mackinnon R Taylor Recent Advances in the Chemistry of Siloxane Polymers

and Copolymers In The Chemistry of Organic Silicon Compounds John Wiley amp Sons Ltd

2003 pp 2217

119 (a) A D Becke J Chem Phys 1993 98 5648 (b) B Miehlich A Savin H Stoll H

Preuss Chem Phys Lett 1989 157 200 (c) Gussian 03 Revision E01 M J Frisch G W

Trucks H B Schlegel G E Scuseria M A Robb J R Cheeseman J A Montgomery Jr

T Vreven K N Kudin J C Burant J M Millam S S Iyengar J Tomasi V Barone B

Mennucci M Cossi G Scalmani N Rega G A Petersson H Nakatsuji M Hada M

Ehara K Toyota R Fukuda J Hasegawa M Ishida T Nakajima Y Honda O Kitao H

Nakai M Klene X Li J E Knox H P Hratchian J B Cross V Bakken C Adamo J

Jaramillo R Gomperts R E Stratmann O Yazyev A J Austin R Cammi C Pomelli J W

Ochterski P Y Ayala K Morokuma G A Voth P Salvador J J Dannenberg V G

Zakrzewski S Dapprich A D Daniels M C Strain O Farkas D K Malick A D Rabuck

K Raghavachari J B Foresman J V Ortiz Q Cui A G Baboul S Clifford J Cioslowski

B B Stefanov G Liu A Liashenko P Piskorz I Komaromi R L Martin D J Fox T

References

- 135 -

Keith M A Al-Laham C Y Peng A Nanayakkara M Challacombe P M W Gill B

Johnson W Chen M W Wong C Gonzalez and J A Pople Gaussian Inc Wallingford

CT 2004

120 M Denk R K Hayashi R West Chem Commun 1994 33

121 L Kong J Zhang H Song C Cui Dalton Trans 2009 5444

122 A Meltzer S Inoue C Praumlsang M Driess J Am Chem Soc 2010 132 3038

123 P Macchi D M Proserpio A Sironi J Am Chem Soc 1998 120 1447

124 (a) M Regitz O J Scherer Multiple bonds and Low Coordination in Phosphorus Chemistry

New York 1990 p 5 (b) M Driess Coord Chem Rev 1995 145 1 (c) V Y Lee A

Sekiguchi J Escudieacute H Ranaivonjatovo Chem Lett 2010 39 312

125 C N Smit F M Lock F Bickelhaupt Tetrahedron Lett 1984 25 3011

126 (a) C N Smit F Bickelhaupt Organometallics 1987 6 1156 (b) E Niecke E Klein M

Nieger Angew Chem Int Ed 1989 28 751 (c) R Corriu G Lanneau C Priou Angew

Chem Int Ed 1991 30 1130 (d) M Driess Angew Chem Int Ed 1991 30 1022 (e) H R

G Bender E Niecke M Nieger J Am Chem Soc 1993 115 3314 (f) M Driess S Rell

H Pritzkow Chem Commun 1995 253 (g) M Driess H Pritzkow S Rell U Winkler

Organometallics 1996 15 1845 (h) M Driess S Block M Brym M T Gamer Angew

Chem Int Ed 2006 45 2293 (i) S Yao S Block M Brym M Driess Chem Commun

2007 3844 (j) V Y Lee M Kawai A Sekiguchi H Ranaivonjatovo J Escudieacute

Organometallics 2009 28 6625 (k) B Li T Matsuo D Hashizume H Fueno K Tanaka

K Tamao J Am Chem Soc 2009 131 13222

127 (a) C H Lai M D Su S Y Chu Inorg Chem 2002 41 1320 (b) R Pietschnig A

Orthaber Eur J Inorg Chem 2006 4570 (c) C H Chen M D Su Eur J Inorg Chem

2008 1241 (d) V Lattanzi S Thorwirth D T Halfen L A Mueck L M Ziurys P

Thaddeus J Gauss M C Mccarthy Angew Chem Int Ed 2010 49 5661

128 S Inoue W Wang C Praumlsang M Asay E Irran M Driess J Am Chem Soc 2011 133

2868

129 (a) R Appel W A Paulen Angew Chem Int Ed 1981 20 869 (b) V Cappello J

Baumgartner A Dransfeld K Hassler Eur J Inorg Chem 2006 4589

130 M Igarashi M Ichinohe A Sekiguchi J Am Chem Soc 2007 129 12660

131 F A Cotton G Wilkinson C Murillo M Bochmann Advanced Inorganic Chemistry 1999

132 (a) N Wiberg C M M Finger K Polborn Angew Chem Int Ed 1993 32 1054 (b) M

Ichinohe M Toyoshima R Kinjo A Sekiguchi J Am Chem Soc 2003 125 13328

133 (a) A J Arduengo H V R Dias J C Calabrese F Davidson Inorg Chem 1993 32 1541

(b) N Kuhn T Kratz D Blaumlser R Boese Chem Ber 1995 128 245 (c) P A Rupar M C

Jennings K M Baines Organometallics 2008 27 5043 (d) A J Ruddy P A Rupar K J

Bladek C J Allan J C Avery K M Baines Organometallics 2010 29 1362

134 A Schaumlfer W Saak M Weidenbruch H Marsmann G Henkel Chem Ber 1997 130 1733

135 (a) D Morales-Morales C Grause K Kasaoka R O Redoacuten R E Cramer C M Jensen

Inorg Chim Acta 2000 300ndash302 958 (b) T Kimura Y Uozumi Organometallics 2006 25

4883 (c) R B Bedford M Betham J P H Charmant M F Haddow A G Orpen L T

Pilarski S J Coles M B Hursthouse Organometallics 2007 26 6346 (d) J Aydin K S

Kumar L Eriksson K J Szaboacute Adv Syn Catal 2007 349 2585 (e) J-F Gong Y-H

References

- 136 -

Zhang M-P Song C Xu Organometallics 2007 26 6487 (f) R A Baber R B Bedford

M Betham M E Blake S J Coles M F Haddow M B Hursthouse A G Orpen L T

Pilarski P G Pringle R L Wingad Chem Commun 2006 3880 (g) A V Polukeev S A

Kuklin P V Petrovskii S M Peregudova A F Smolyakov F M Dolgushin A A

Koridze Dalton Trans 2011 40 7201 (h) R B Bedford Y-N Chang M F Haddow C L

Mcmullin Dalton Trans 2011 40 9034

136 (a) C Watanabe T Iwamoto C Kabuto M Kira Angew Chem Int Ed 2008 47 5386 (b)

C Watanabe Y Inagawa T Iwamoto M Kira Dalton Trans 2010 39 9414

137 (a) G Tavcar S S Sen R Azhakar A Thorn H W Roesky Inorg Chem 2010 49 10199

(b) R Azhakar S P Sarish H W Roesky J Hey D Stalke Inorg Chem 2011 50 5039

138 W Chen P J Mccormack K Mohammed W Mbafor S M Roberts J Whittall Angew

Chem Int Ed 2007 46 4141

139 (a) T Sasamori A Yuasa Y Hosoi Y Furukawa N Tokitoh Organometallics 2008 27

3325 (b) T Sasamori A Yuasa Y Hosoi Y Furukawa N Tokitoh Bull Chem Soc Jpn

2009 82 793

140 (a) F Baumann E Dormann Y Ehleiter W Kaim J Kaumlrcher M Kelemen R Krammer D

Saurenz D Stalke C Wachter G Wolmershaumluser H Sitzmann J Organomet Chem 1999

587 267 (b) F Hung-Low C A Bradley Organometallics 2011 30 2636 (c) F Hung-Low

J P Krogman J W Tye C A Bradley Chem Commun 2012 48 368

141 R Azhakar R S Ghadwal H W Roesky J Hey D Stalke Chem Asian J 2012 7 528

142 R S Ghadwal R Azhakar K ProPper J J Holstein B Dittrich H W Roesky Inorg

Chem 2011 50 8502

143 J Li S Merkel J Henn K Meindl A DoRing H W Roesky R S Ghadwal D Stalke

Inorg Chem 2010 49 775

144 M Ingleson H Fan M Pink J Tomaszewski K G Caulton J Am Chem Soc 2006 128

1804

145 A Schnepf Z Anorg Allg Chem 2006 632 935

146 (a) M D Rausch R A Genetti J Org Chem 1970 35 3888 (b) F Ungvary A Sisak L

Markoacute J Organomet Chem 1980 188 373

147 (a) E Erdik Tetrahedron 1992 48 9577 (b) P Knochel R D Singer Chem Rev 1993 93

2117 (c) M Rottlaumlnder P Knochel Tetrahedron Lett 1997 38 1749

148 (a) H Boumlnnemann Angew Chem Int Ed 1978 17 505 (b) K P C Vollhardt Angew Chem

Int Ed 1984 23 539 (c) H Boumlnnemann Angew Chem Int Ed 1985 24 248 (d) W Hess

J Treutwein G Hilt Synthesis 2008 2008 3537 (e) C J Scheuermann B D Ward New J

Chem 2008 32 1850 (f) T Shibata K Tsuchikama Org Biomol Chem 2008 6 1317 (g)

K Tanaka Chem Asian J 2009 4 508 (h) J A Varela C Saaacute Synlett 2008 2008 2571

149 (a) G Hilt C Hengst W Hess Eur J Org Chem 2008 2008 2293 (b) A Geny N Agenet

L Iannazzo M Malacria C Aubert V Gandon Angew Chem Int Ed 2009 48 1810 (c)

C C Eichman J P Bragdon J P Stambuli Synlett 2011 2011 1109

150 (a) Y Wakatsuki H Yamazaki Bull Chem Soc Jpn 1985 58 2715 (b) Y B Taarit Y

Diab B Elleuch M Kerkani M Chihaoui Chem Commun 1986 402 (c) H Nehl Chem

Ber 1994 127 2535 (d) C Wang X Li F Wu B Wan Angew Chem Int Ed 2011 50

7162

References

- 137 -

151 G M Sheldrick SHELX-97 Program for Crystal Structure Determination Universitaumlt

Goumlttingen (Germany) 1997

152 P Schlack G Keil Justus Liebigs Annalen der Chemie 1963 661 72

Appendix

- 138 -

7 APPENDIX

71 Abbreviations

Ada adamantanyl MHz Megahertz

Ar aryl min minute(s)

mmol millimole(ar)

MS mass spectrometry

B3LYP Beckersquos three-parameter hybrid

functional using the Lee Yang

and Parr correlation ldquofunctionalrdquo MW molecular weight

BINAP 22rsquo-(Ph2P)2-11rsquo-binaphthyl mz masscharge

br broad nacnac HC(MeC=N-Dip) 2minus

tBu tert-butyl Naph naphthyl

degC Celsius degree NBO natural bond orbital

ca about NHC N-Heterocyclic Carbene

calc calculated NICS nucleus independent chemical shift

CBD cyclobutadiene NMR Nuclear Magnetic Resonance

cod COD 15-cyclooctadiene NPA natural population analysis

Cp cyclopentadienyl Ph phenyl

d doublet ppm parts per million

DCM dichloromethane iPr iso-propyl

DFT density functional theory q quartet

Dip 26-iPr2C6H3 R organic substituent

EI electron impact ionization RT room temperature

equiv equivalent(s) s singlet strong

ESI electrospray ionization sept septet

Et ethyl t triplet

eV electronvolt THF tetrahydrofuran

Fc ferrocendiyl Tip 246-iPr2C6H2

g gram(s) TMEDA tetramethylethyldiamine

h hour(s) TMS tetramethylsilane

HOMO highest occupied molecular orbital TS transition state

Hz Hertz TZVP triple-zeta valence polarization

IR infrared

K Kelvin

TZVDP TZVP two sets of polarization

functions aL PhC(

tBuN)2

minus UV-vis ultraviolet-visible

VE valence electron LUMO lowest unoccupied molecular

orbital vs very strong

M Metal VT variable temperature

m multiplet medium w weak

Me methyl WBI Wiberg Bond Index

Mes mesityl 246-Me3-C6H2 δ chemical shift

Appendix

- 139 -

GeN

N

GeN

Dip

Dip

DipCl

N

SnN

Dip

Dip

GeNN

SnN

Dip

DipDip

N

Dip

6 7

72 Index of compounds discussed in this dissertation

1 2 3 4

5 8 9

10 11 12 13 14

15 16 17 18

19 20 21 22

Appendix

- 140 -

23 24 25 26

27 28 29

30 31 32 33

34 35 36

tBu

N

N

tBu

Ph

Si

Cl

37 38 39 40

Appendix

- 141 -

tBu

N

N

tBu

PhSi

tBu

N

N

tBu

Ph Si

Co

Fe

41 42 43

44 45 46

47a 47b 48a 48b

Appendix

- 142 -

73 Crystal Data and Refinement Details

Table 731 Crystal data and refinement

Compound 3 4 5

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group

Unit cell dimensions

a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z

Density (calc) (gcm3)

Absorp Coeffic (mm-1

)

F(000)

Crystal size (mm3)

θ range for data collec

Index ranges

Reflections collected

Independent reflections

Completeness to θ = 2500deg

Absorption correction

Max amp min transmission

Refinement method

Data restraints parameters

Goodness of fit on F2

Final R indices [Igt2σ(I)]

R indices (all data)

Largest peak amp hole (eAring-3

)

C50 H88 Ge2 K2 N2 O4

100460

150(2)

71073

Triclinic

P-1

106989(7) pm

114137(7) pm

122625(8) pm

74158(6) deg

76395(6) deg

83400(5) deg

139807(16)

1

1193

1263

536

028 x 02 x 018

326 to 2500deg

-12lt=hlt=12

-13lt=klt=13

-14lt=llt=14

12268

4910 [R(int) = 00358]

996

Semi-empirical from equiv

100000 and 094847

Full-matrix least-squares on F2

4910 0 281

0940

R1 = 00328 wR2 = 00638

R1 = 00538 wR2 = 00666

0456 and -0223

C41 H5 Ge N3

66650

150(2)

71073

Triclinic

P-1

91129(6) pm

113531(7) pm

190282(10) pm

100360(5) deg

101854(5) deg

98627(5) deg

185918(19)

2

1191

0855

716

039 x 012 x 007

297 to 2500deg

-10lt=hlt=10

-13lt=klt=13

-22lt=llt=22

14570

6543 [R(int) = 00560]

998


0943 and 0777


6543 0 420

0785

R1 = 00399 wR2 = 00513

R1 = 00853 wR2 = 00566

0577 and -0317

C66 H102 Ge4 K2 N4 O2

135208

150(2)

71073

Monoclinic

P21n

12370(3) pm

148433(14) pm

188725(19) pm

90059(8)deg

96311(14)deg

90082(13)deg

34442(10)

2

1304

1892

1416

030 x 025 x 015

292 to 2500deg

-14lt=hlt=14

-15lt=klt=17

-14lt=llt=22

17371

6032 [R(int) = 00487]

995

Analytical

0807 and 0584


6032 2 364

0911

R1 = 00424 wR2 = 00801

R1 = 00874 wR2 = 00885

0497 and -0457

Appendix

- 143 -


Compound 6 8 12

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C46 H65 Ge2 N3

80519

150(2)

71073

Monoclinic

C2c

44536(2) pm

98204(5) pm

218135(10) pm

90deg

116030(4)deg

90deg

85727(7)

8

1248

1436

3408

038 x 024 x 010

305 to 2500deg

-49lt=hlt=52

-10lt=klt=11

-24lt=llt=25

20162

7493 [R(int) = 00954]

992


100000 and 074676


7493 0 476

0917

R1 = 00559 wR2 = 00778

R1 = 01461 wR2 = 00966

0590 and -0578

C46 H65 Ge N3 Sn

85129

150(2)

71073

Triclinic

P-1

867780(10) pm

120514(4) pm

210797(6) pm

96333(2)deg

97393(2)deg

99141(2)deg

213908(10)

2

1322

1320

888

016 x 014 x 012

295 to 2500deg

-10lt=hlt=10

-14lt=klt=14

-25lt=llt=25

16936

7496 [R(int) = 00251]

994


100000 and 099037


7496 0 495

1001

R1 = 00309 wR2 = 00706

R1 = 00437 wR2 = 00733

1468 and -0424

C37 H48 N2

52077

150(2)

71073

Triclinic

P-1

108485(5) pm

127284(7) pm

132348(4) pm

65748(4)deg

86290(3)deg

71699(5)deg

157759(12)

2

1096

0063

568

029 x 022 x 018

298 to 2500deg

-11lt=hlt=12

-15lt=klt=15

-15lt=llt=15

13428

5541 [R(int) = 00203]

998

None

09888 and 09820


5541 0 364

1029

R1 = 00439 wR2 = 00900

R1 = 00633 wR2 = 00963

0188 and -0193

Appendix

- 144 -


Compound 14 16 17

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C37 H46 Cl Ge N2

62680

150(2)

71073

Monoclinic

P21c

117621(2) pm

175495(4) pm

166051(3) pm

90deg

107053(2)deg

90deg

327691(11)

4

1270

1044

1324

040 x 032 x 022

342 to 2500deg

-13lt=hlt=13

-19lt=klt=20

-19lt=llt=18

16923

5742 [R(int) = 00250]

997


100000 and 082078


5742 0 378

1044

R1 = 00328 wR2 = 00709

R1 = 00496 wR2 = 00742

0736 and -0362

C37 H46 Ge N2

59135

150(2)

71073

Triclinic

P-1

108388(6) pm

127885(7) pm

132778(4) pm

66971(4)deg

85749(3)deg

71833(5)deg

160695(13)

2

1222

0980

628

029 x 015 x 007

307 to 2500deg

-12lt=hlt=12

-15lt=klt=15

-15lt=llt=15

13501

5636 [R(int) = 00366]

996


100000 and 092510


5636 0 369

1031

R1 = 00489 wR2 = 01180

R1 = 00691 wR2 = 01242

0539 and -0501

C37 H49 Ge N3

60838

150(2)

71073

Monoclinic

P21c

117714(4) pm

174309(6) pm

166868(6) pm

90deg

106866(4)deg

90deg

32766(2)

4

1233

0964

1296

030 x 023 x 019

342 to 2500deg

-8lt=hlt=13

-10lt=klt=20

-19lt=llt=16

12816

5749 [R(int) = 00325]

998


100000 and 095425


5749 0 378

1060

R1 = 00464 wR2 = 01084

R1 = 00699 wR2 = 01133

1717 and -0738

Appendix

- 145 -


Compound 18 20 22

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C37 H48 Ge N2 O

60936

150(2)

71073

Monoclinic

P21c

117560(3) pm

174116(5) pm

166421(4) pm

90deg

106992(3)deg

90deg

325778(15)

4

1242

0971

1296

031 x 014 x 005

343 to 2500deg

-13lt=hlt=13

-20lt=klt=20

-19lt=llt=19

23624

5720 [R(int) = 00371]

998


100000 and 083390


5720 0 379

1018

R1 = 00336 wR2 = 00752

R1 = 00516 wR2 = 00789

0521 and -0366

C28 H38 N2

40260

150(2)

71073

Monoclinic

P21c

94924(4) pm

256583(9) pm

107465(5) pm

90deg

110403(5)deg

90deg

245320(18)

4

1090

0063

880

017 x 015 x 013

343 to 2500deg

-11lt=hlt=10

-30lt=klt=27

-12lt=llt=11

8561

4313 [R(int) = 00209]

997


100000 and 099057


4313 0 281

1041

R1 = 00476 wR2 = 01015

R1 = 00771 wR2 = 01083

0253 and -0194

C28 H37 Cl Ge N2 O

52564

150(2)

71073

Triclinic

P-1

89021(3) pm

107319(4) pm

151176(6) pm

75734(4)deg

74781(3)deg

75311(3)deg

132282(8)

2

1320

1281

552

020 x 012 x 008

354 to 2500deg

-10lt=hlt=10

-12lt=klt=12

-15lt=llt=17

9246

4654 [R(int) = 00211]

997


100000 and 086160


4654 0 304

0946

R1 = 00274 wR2 = 00579

R1 = 00386 wR2 = 00597

0394 and -0264

Appendix

- 146 -


Compound 23 27 28

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C28 H36 Cl2 Ge N2

54408

150(2)

71073

Monoclinic

C2c

279616(13) pm

113538(3) pm

177729(7) pm

90deg

109718(5)deg

90deg

53115(4)

8

1361

1374

2272

021 x 017 x 015

332 to 2500deg

-25lt=hlt=33

-7lt=klt=13

-21lt=llt=20

10951

4663 [R(int) = 00459]

997


100000 and 091223


4663 0 304

0856

R1 = 00372 wR2 = 00584

R1 = 00684 wR2 = 00620

0589 and -0533

C30 H48 Cl2 N4 O Si2

60780

150(2)

71073

Monoclinic

P21c

121593(5) pm

162045(6) pm

171248(7) pm

90deg

98177(4)deg

90deg

33399(2)

4

1209

0295

1304

030 x 015 x 005

335 to 2500deg

-14lt=hlt=13

-16lt=klt=19

-20lt=llt=20

23741

5865 [R(int) = 00491]

998


100000 and 086688


5865 172 490

1035

R1 = 00543 wR2 = 01080

R1 = 00905 wR2 = 01194

0310 and -0412

C30 H46 N4 O Si2

53489

150(2)

71073

Orthorhombic

Fdd2

31188(2) pm

39120(3) pm

102620(6) pm

90deg

90deg

90deg

125204(14)

16

1135

0141

4640

031 x 011 x 007

334 to 2500deg

-28lt=hlt=36

-46lt=klt=45

-12lt=llt=12

11517

4372 [R(int) = 00656]

997


100000 and 097469


4372 1 346

0897

R1 = 00488 wR2 = 00604

R1 = 00754 wR2 = 00650

0328 and -0229

Appendix

- 147 -


Compound 29 30 31

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C38 H58 N4 Ni O Si2

70177

150(2)

71073

Triclinic

P-1

98776(8) pm

129530(11) pm

155488(13) pm

81634(7)deg

83316(7)deg

82826(7)deg

19430(3)

2

1200

0594

756

020 x 009 x 007

330 to 2500deg

-11lt=hlt=11

-15lt=klt=13

-18lt=llt=18

14961

6828 [R(int) = 00414]

997


100000 and 091998


6828 0 474

0948

R1 = 00386 wR2 = 00807

R1 = 00605 wR2 = 00853

0407 and -0240

C21 H41 N2 P Si3

43680

173(2)

71073

Orthorhombic

Pbca

193556(7) pm

142399(4) pm

199777(6) pm

90deg

90deg

90deg

55063(3)

8

1054

0239

1904

039 x 036 x 016

351 to 2500deg

-13lt=hlt=23

-16lt=klt=16

-23lt=llt=22

19912

4836 [R(int) = 00961]

998


09627 and 09125


4836 18 287

0906

R1 = 00571 wR2 = 00889

R1 = 01270 wR2 = 01032

0316 and -0214

C44 H60 N4 P2 Si2

76308

173(2)

71073

Monoclinic

C2c

23841(3) pm

101993(12) pm

19369(2) pm

90deg

108346(12)deg

90deg

44703(9)

4

1134

0184

1640

076 x 057 x 055

353 to 2500deg

-28lt=hlt=28

-12lt=klt=12

-20lt=llt=23

16197

3927 [R(int) = 00447]

997


09053 and 08725


3927 0 251

1034

R1 = 00618 wR2 = 01393

R1 = 00843 wR2 = 01489

0721 and -0649

Appendix

- 148 -


Compound 33 36 40-endo

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C56 H98 Cl4 N6 Si6 Sn2

140312

150(2)

71073

Triclinic

P-1

105159(4) pm

127622(6) pm

269391(12) pm

90310(4)deg

90855(3)deg

102927(3)deg

35232(3)

2

1323

1000

1456

013 x 012 x 009

336 to 2500deg

-12lt=hlt=12

-15lt=klt=15

-29lt=llt=32

25757

12396 [R(int) = 00546]

997


09154 and 08810


12396 536 816

2077

R1 = 01231 wR2 = 01906

R1 = 01495 wR2 = 01944

1510 and -4753

C91 H139 N8 O4 Pd Si4

162786

150(2)

71073

Triclinic

P-1

145970(8) pm

151441(15) pm

232982(16) pm

71358(8)deg

74666(5)deg

85365(6)deg

47063(6)

2

1149

0298

1750

019 x 013 x 011

327 to 2500deg

-17lt=hlt=17

-17lt=klt=18

-27lt=llt=27

41022

16531 [R(int) = 00735]

998


09679 and 09455


16531 284 1112

0908

R1 = 00558 wR2 = 01021

R1 = 01075 wR2 = 01128

0688 and -0448

C40 H54 Fe Ge2 N4

79190

150(2)

71073

Monoclinic

P21n

10532(3) pm

20258(5) pm

18990(5) pm

90deg

10542(3)deg

90deg

39060(19)

4

1347

1927

1648

012 x 008 x 005

322 to 2500deg

-6lt=hlt=12

-22lt=klt=24

-22lt=llt=21

16887

6870 [R(int) = 01353]

997


100000 and 073478


6870 213 498

1044

R1 = 00912 wR2 = 01786

R1 = 01680 wR2 = 02282

0570 and -1404

Appendix

- 149 -


Compound 40-exo 41 42

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C40 H54 Fe Ge2 N4

79190

150(2)

71073

Monoclinic

P21n

165582(11) pm

127695(7) pm

198175(12) pm

90deg

107428(7)deg

90deg

39979(4)

4

1316

1883

1648

012 x 011 x 009

337 to 2499deg

-16lt=hlt=19

-15lt=klt=15

-23lt=llt=23

29049

7015 [R(int) = 00329]

998


100000 and 052405


7015 0 436

1065

R1 = 00263 wR2 = 00574

R1 = 00318 wR2 = 00595

0357 and -0360

C45 H59 Co Fe N4 Si2

82692

150(2)

71073

Monoclinic

P21c

119176(7) pm

160794(9) pm

220424(13) pm

90deg

94402(5)deg

90deg

42115(4)

4

1304

0831

1752

015 x 013 x 007

323 to 2500deg

-14lt=hlt=14

-19lt=klt=17

-16lt=llt=26

17786

7404 [R(int) = 01111]

998


100000 and 075122


7404 0 490

1052

R1 = 00717 wR2 = 01045

R1 = 01208 wR2 = 01181

0467 and -0370

C45 H59 Co Fe Ge2 N4

91592

150(2)

71073

Monoclinic

P21c

121662(3) pm

160596(3) pm

220073(5) pm

90deg

93549(2)deg

90deg

429163(16)

4

1418

2134

1896

015 x 011 x 008

336 to 2500deg

-14lt=hlt=14

-19lt=klt=19

-26lt=llt=26

33743

7539 [R(int) = 00521]

998


100000 and 068509


7539 0 521

1259

R1 = 00400 wR2 = 00965

R1 = 00536 wR2 = 01000

0376 and -0373

Appendix

- 150 -

Atomic coordinates of four unpublished compounds 20 22 23 and 33 are shown in

following tables

Table 739 Atomic coordinates (times10

4) and equivalent isotropic displacement parameters (Aring

2times10

3)

for 20 U(eq) is defined as one third of the trace of the orthogonalized Uij tensor

x y z U(eq)

N(1) 1159(1) 1176(1) 6836(1) 20(1)

C(1) 1706(2) 1650(1) 6995(1) 21(1)

N(2) -1293(2) 1547(1) 7057(1) 23(1)

C(2) 789(2) 2089(1) 7078(1) 20(1)

C(3) -626(2) 2021(1) 7158(1) 20(1)

C(4) 3331(2) 1741(1) 7112(2) 29(1)

C(5) 3920(2) 2283(1) 7590(2) 34(1)

C(6) 2795(2) 2681(1) 6772(2) 35(1)

C(7) 1375(2) 2643(1) 7102(2) 27(1)

C(8) -1522(2) 2482(1) 7295(2) 21(1)

C(9) -2759(2) 2643(1) 6227(2) 27(1)

C(10) -3571(2) 3077(1) 6331(2) 33(1)

C(11) -3169(2) 3358(1) 7498(2) 35(1)

C(12) -1948(2) 3199(1) 8573(2) 32(1)

C(13) -1133(2) 2765(1) 8467(2) 27(1)

C(14) -2537(2) 1417(1) 7503(2) 35(1)

C(15) -3250(3) 920(1) 6823(2) 61(1)

C(16) -1974(3) 1344(1) 9002(2) 65(1)

C(17) 2080(2) 741(1) 6834(2) 20(1)

C(18) 2353(2) 597(1) 5670(2) 23(1)

C(19) 3237(2) 160(1) 5724(2) 29(1)

C(20) 3821(2) -131(1) 6867(2) 32(1)

C(21) 3480(2) -1(1) 7977(2) 29(1)

C(22) 2598(2) 427(1) 7984(2) 23(1)

C(23) 2150(2) 562(1) 9174(2) 28(1)

C(24) 2101(2) 91(1) 10028(2) 39(1)

C(25) 3156(2) 987(1) 10029(2) 42(1)

C(26) 1602(2) 885(1) 4374(2) 29(1)

C(27) 2645(3) 974(1) 3586(2) 53(1)

C(28) 195(3) 588(1) 3539(2) 54(1)

Appendix

- 151 -

Table 7310 Atomic coordinates (times104) and equivalent isotropic displacement parameters (Aring

2times10

3)


x y z U(eq)

Ge(1) 4751(1) 5279(1) 3913(1) 24(1)

Cl(1) 4863(1) 7474(1) 3443(1) 35(1)

O(1) 2591(1) 5468(1) 4187(1) 20(1)

N(1) 4469(2) 5098(1) 2623(1) 17(1)

C(1) 3006(2) 5278(2) 2582(1) 16(1)

N(2) 1482(2) 7765(2) 2375(1) 20(1)

C(2) 2432(2) 5062(2) 1801(1) 21(1)

C(3) 1144(2) 4228(2) 2174(2) 31(1)

C(4) -158(2) 4793(2) 2933(2) 30(1)

C(5) 534(2) 4844(2) 3741(1) 21(1)

C(6) 1810(2) 5684(2) 3440(1) 17(1)

C(7) 1063(2) 7152(2) 3205(1) 18(1)

C(8) 820(2) 9172(2) 2096(1) 26(1)

C(9) 397(3) 9344(2) 1159(2) 40(1)

C(10) 2058(3) 9950(2) 2035(2) 43(1)

C(11) -95(2) 7719(2) 3998(1) 18(1)

C(12) 434(2) 8108(2) 4652(1) 22(1)

C(13) -648(2) 8637(2) 5376(1) 27(1)

C(14) -2259(2) 8769(2) 5459(2) 30(1)

C(15) -2795(2) 8370(2) 4815(2) 30(1)

C(16) -1724(2) 7845(2) 4085(1) 24(1)

C(17) 5786(2) 4690(2) 1889(1) 19(1)

C(18) 6546(2) 3361(2) 1997(1) 22(1)

C(19) 7868(2) 3005(2) 1310(2) 28(1)

C(20) 8423(2) 3902(2) 552(2) 29(1)

C(21) 7656(2) 5209(2) 464(1) 26(1)

C(22) 6329(2) 5635(2) 1128(1) 21(1)

C(23) 5549(2) 7085(2) 991(2) 26(1)

C(24) 6701(3) 7932(2) 989(2) 41(1)

C(25) 4931(3) 7520(2) 84(2) 40(1)

C(26) 6001(2) 2315(2) 2820(2) 27(1)

C(27) 5775(3) 1139(2) 2495(2) 40(1)

C(28) 7175(3) 1863(2) 3471(2) 38(1)

Appendix

- 152 -


2times10

3)


x y z U(eq)

Ge(1) 967(1) 7605(1) 1823(1) 18(1)

Cl(1) 1020(1) 9314(1) 2345(1) 29(1)

N(1) 1401(1) 6550(2) 2449(1) 19(1)

C(1) 1534(1) 5601(2) 2029(2) 16(1)

Cl(2) 198(1) 7116(1) 1640(1) 31(1)

N(2) 1101(1) 7630(2) 909(1) 15(1)

C(2) 1548(1) 5691(2) 1285(2) 15(1)

C(3) 1442(1) 6764(2) 777(2) 14(1)

C(4) 1615(1) 6867(2) 172(2) 19(1)

C(5) 1945(1) 5989(2) -42(2) 26(1)

C(6) 2098(1) 4966(2) 547(2) 22(1)

C(7) 1669(1) 4652(2) 844(2) 21(1)

C(8) 1625(1) 4444(2) 2470(2) 17(1)

C(9) 1229(1) 3875(2) 2611(2) 23(1)

C(10) 1291(1) 2785(2) 2983(2) 29(1)

C(11) 1764(2) 2263(3) 3232(2) 32(1)

C(12) 2169(1) 2832(3) 3121(2) 30(1)

C(13) 2101(1) 3920(2) 2737(2) 22(1)

C(14) 1621(1) 6630(2) 3327(2) 20(1)

C(15) 1219(1) 6848(3) 3699(2) 32(1)

C(16) 2052(1) 7524(2) 3583(2) 34(1)

C(17) 833(1) 8395(2) 248(2) 17(1)

C(18) 1019(1) 9542(2) 207(2) 19(1)

C(19) 745(1) 10248(3) -431(2) 29(1)

C(20) 315(1) 9844(3) -1011(2) 36(1)

C(21) 147(1) 8718(3) -973(2) 33(1)

C(22) 399(1) 7960(2) -350(2) 20(1)

C(23) 215(1) 6700(2) -377(2) 23(1)

C(24) 329(1) 6020(3) -1045(2) 34(1)

C(25) -341(1) 6612(3) -475(2) 31(1)

C(26) 1517(1) 10001(2) 789(2) 22(1)

C(27) 1914(1) 10083(3) 375(2) 32(1)

C(28) 1463(1) 11198(2) 1144(2) 36(1)

Appendix

- 153 -


2times10

3)


x y z U(eq)

Sn(1) 4689(1) 4918(1) 3222(1) 24(1)

Sn(2) 5822(1) 5994(1) 1674(1) 30(1)

Cl(1) 4488(3) 6215(2) 3883(1) 38(1)

Cl(2) 3266(2) 3378(2) 3638(1) 39(1)

Cl(3) 7188(2) 7769(2) 1449(1) 43(1)

Cl(4) 6104(3) 5090(3) 888(1) 57(1)

Si(1) 6825(2) 4259(2) 3587(1) 17(1)

Si(2) 8610(3) 6420(2) 3531(1) 28(1)

Si(3) 9814(2) 4466(2) 3664(1) 26(1)

Si(4) 3648(2) 6680(2) 1375(1) 21(1)

Si(5) 1981(3) 4463(2) 1299(1) 30(1)

Si(6) 649(3) 6348(2) 1247(1) 30(1)

N(1) 6586(7) 2924(5) 3299(3) 20(2)

N(2) 6484(6) 3264(5) 4080(3) 16(2)

N(3) 8389(7) 5001(5) 3582(3) 23(2)

N(4) 3751(7) 7937(6) 1722(3) 22(2)

N(5) 3959(8) 7800(6) 936(3) 27(2)

N(6) 2102(7) 5865(6) 1329(3) 24(2)

C(1) 6258(8) 2470(7) 3742(4) 24(2)

C(2) 5630(8) 1296(7) 3832(3) 20(2)

C(3) 4328(9) 879(7) 3742(4) 30(2)

C(4) 3826(11) -209(8) 3826(4) 44(3)

C(5) 4613(12) -855(8) 3977(4) 47(3)

C(6) 5921(13) -450(9) 4064(4) 54(3)

C(7) 6446(10) 640(8) 3992(4) 36(3)

C(8) 6469(9) 2487(7) 2787(3) 22(2)

C(9) 7183(11) 3385(8) 2465(4) 43(3)

C(10) 5041(10) 2180(9) 2612(4) 44(3)

C(11) 7093(12) 1524(8) 2741(4) 49(3)

C(12) 6251(9) 3286(8) 4625(3) 26(2)

C(13) 4851(10) 2720(9) 4759(4) 48(3)

C(14) 7218(10) 2783(8) 4908(4) 39(3)

C(15) 6455(10) 4474(7) 4759(4) 31(2)

C(16) 7585(10) 6750(8) 3014(4) 43(3)

C(17) 8192(11) 7005(8) 4123(4) 44(3)

C(18) 10317(10) 7108(8) 3367(5) 55(4)

C(19) 10809(9) 4684(9) 3087(4) 39(3)

C(20) 9461(9) 3008(7) 3775(4) 30(2)

Appendix

- 154 -

C(21) 10726(10) 5062(9) 4232(4) 41(3)

C(22) 4144(9) 8514(7) 1315(3) 22(2)

C(23) 4603(10) 9700(7) 1286(3) 30(2)

C(24) 5918(10) 10173(8) 1332(4) 36(3)

C(25) 6315(12) 11289(9) 1292(4) 46(3)

C(26) 5453(14) 11926(9) 1203(4) 50(3)

C(27) 4158(14) 11457(9) 1158(4) 52(3)

C(28) 3726(12) 10336(8) 1194(4) 41(3)

C(29) 3829(9) 8261(7) 2260(3) 24(2)

C(30) 3041(13) 9101(10) 2358(4) 65(4)

C(31) 3223(10) 7251(8) 2537(4) 41(3)

C(32) 5223(10) 8649(10) 2438(4) 59(4)

C(33) 4252(10) 7910(8) 398(3) 30(2)

C(34) 3489(13) 8669(11) 158(4) 67(4)

C(35) 3812(13) 6813(9) 170(4) 60(4)

C(36) 5705(11) 8321(11) 315(4) 63(4)

C(37) 3040(11) 4003(8) 1778(4) 49(3)

C(38) 2431(11) 4059(8) 669(4) 44(3)

C(39) 310(10) 3713(8) 1447(5) 48(3)

C(40) -433(9) 5964(9) 1795(4) 43(3)

C(41) 921(10) 7835(9) 1209(4) 48(3)

C(42) -186(11) 5795(10) 650(4) 57(4)

C(43) -180(17) 209(14) 3445(7) 59(3)

C(44) -1099(17) -417(14) 3132(7) 58(3)

C(45) -949(16) -322(14) 2634(7) 58(2)

C(46) 75(15) 387(13) 2440(7) 58(2)

C(47) 979(17) 1008(14) 2750(6) 60(2)

C(48) 829(17) 908(15) 3251(7) 60(3)

C(49) 210(20) 473(17) 1887(7) 58(3)

C(43A) 798(17) 917(14) 2044(7) 58(3)

C(44A) 1381(17) 1418(14) 2465(7) 59(3)

C(45A) 931(16) 1088(14) 2929(7) 59(3)

C(46A) -134(15) 231(13) 2969(7) 58(2)

C(47A) -748(17) -263(14) 2547(6) 58(2)

C(48A) -289(17) 75(14) 2084(7) 58(2)

C(49A) -640(20) -111(17) 3469(8) 60(3)

C(50) 120(20) -463(18) -179(10) 106(6)

C(51) -640(30) -620(20) 236(10) 106(6)

C(52) -730(20) 250(20) 530(10) 107(6)

C(53) -70(30) 1260(20) 404(11) 109(6)

C(54) 680(20) 1409(19) -10(11) 107(6)

C(55) 780(30) 558(19) -303(11) 106(6)

C(56) 250(30) -1390(20) -499(12) 120(7)

Appendix

- 155 -

C(57) 575(16) 499(14) 4873(6) 52(3)

C(58) 807(18) -512(14) 4941(8) 53(3)

C(59) -138(17) -1326(14) 5128(7) 55(3)

C(60) -1333(18) -1140(15) 5253(8) 57(3)

C(61) -1572(16) -130(15) 5187(7) 56(3)

C(62) -620(17) 686(15) 5000(8) 53(3)

C(63) 1600(20) 1369(17) 4669(9) 59(5)

Appendix

- 156 -

74 Publications in this dissertation

1 Wenyuan Wang Shigeyoshi Inoue Stephan Enthaler and Matthias Driess

Angew Chem Int Ed 2012 51 6167-6171 Angew Chem 2012 124 6271-6275

Bis(silylenyl)- and Bis(germylenyl)-Substituted Ferrocenes Synthesis Structure and Catalytic

Applications of Bidentate Silicon(II)-Cobalt Complex

2 Wenyuan Wang Shigeyoshi Inoue Elisabeth Irran and Matthias Driess


Synthesis and unexpected coordination of a silicon(II)-based SiCSi pincerlike arene to

palladium

3 Wenyuan Wang Shigeyoshi Inoue Shenglai Yao and Matthias Driess

Organometallics 2011 30 6490-6494

Reactivity of N-Heterocyclic germylene toward ammonia and water

4 Shenglai Yao Yun Xiong Wenyuan Wang and Matthias Driess

Chem Eur J 2011 17 4890-4895

Synthesis structure and reactivity of a pyridine-stabilized germanone

5 Shigeyoshi Inoue Wenyuan Wang Carsten Praesang Matthew Asay Elisabeth Irran and

Matthias Driess

J Am Chem Soc 2011 133 2868ndash2871

An ylide-like phosphasilene and striking formation of a 4π-electron resonance-stabilized 24-

disila-13-diphosphacyclobutadiene



An isolable bis-silylene oxide (ldquodisilylenoxanerdquo) and its metal coordination


Chem Commun 2009 2661ndash2663

An unsymmetric substituted digermylene with a Ge(I)ndashGe(I) bond and synthesis of a

germylenendashstannylene with a Ge(I)ndashSn(I) bond

8 Wenyuan Wang Shenglai Yao Christoph van Wuellen and Matthias Driess


A cyclopentadienide analogue containing divalent germanium and a heavy cyclobutadiene-

like dianion with an unusual Ge4 Core

Appendix

- 157 -

75 Curriculum Vitae

Personal Data

Date and Place of Birth 17th

January 1976 in Nei Mongol China

Nationality Chinese

Education

1982-1987 Elementary School in BaoTou City Nei Mongol China

1987-1993 High School in BaoTou City Nei Mongol China

1993-1997 Department of Chemistry Inner Mongolia Normal University (China)

Bachelor Chemistry

071997 Bachelor of Chemistry education

2003-2007 Institut fuumlr Chemie der Technischen Universitaumlt Berlin

Diplom Chemistry Prof Dr Matthias Driess

012008 Diplom of Science Degree


PhD Chemistry Prof Dr Matthias Driess

Herein I affirm that this dissertation was finished independently at the ldquoInstitut fuumlr

Chemierdquo at the ldquoTechnischen Universitaumlt Berlinrdquo under the guidance of

Prof Dr Matthias Driess where all references and additional aid sources have been

appropriately cited

Wenyuan Wang

Berlin Juli 2012

DISSERTATION

by

Dipl Chemiker

Wenyuan Wang

from Nei Mongol (China)






























Table of contents

i

TABLE OF CONTENTS

1 INTRODUCTION 1





2 MOTIVATION 21


























Table of contents

ii






































Table of contents

iii

6 REFERENCES 129

7 APPENDIX 138






Introduction

- 1 -

1 INTRODUCTION






effect[1]













is maximal[4]










Introduction

- 2 -














silanone I3[9]









elements[11]



Introduction

- 3 -








The


Very




The bonding


0 donor-



bonds of ns2rarrp


orbitals[3 12d]





Introduction

- 4 -















and






Ge single[13f]






Introduction

- 5 -


reported by







order of three










species[12c]









(Scheme 16)



Introduction

- 6 -










II



The



[29]) was reported




II and Pb






this work

Introduction

- 7 -










SiIV







With these new





Introduction

- 8 -










The donor














Introduction

- 9 -







I23 with a Si0=Si




I





I











Introduction

- 10 -

I28[40]











reagents[43]


with a Ge0=Ge

0













Introduction

- 11 -






Jambor showed that








compound I32











Introduction

- 12 -




and I41[50]







minus) Nevertheless












synthetic chemists




Surprisingly X-ray



was









Introduction

- 13 -



















Introduction

- 14 -













II halides (ArE





Wright 1997


I52 Lappert 1997

SnNMe2

Sn

Me2N

NR

NR

NN

SiMe3

E

(Me3Si)2N

E

Me3Si

N(SiMe3)2

N

N

SiMe3

Sn

(Me3Si)2N

Sn

Me3Si

N(SiMe3)2

Lappert 1994


NN

N N

SnSn

SiMe3

SiMe3

Me3Si

Me3Si

I53 Lappert 1997

NN

N N

SnSn

SiMe3

SiMe3

Me3Si

Me3Si

Sn

Sn

Power 2005

I56 E = Ge R = Dip

I57 E = Sn R = Tip

R

RE

NH2

E

H2N

R

R








Introduction

- 15 -





and with





germylene I63[64]





(I65-I74) were






(aLSi-O-Si

aL

aL = PhC(

tBuN)2


Introduction

- 16 -


I77[68]


and









II Pb

II like I79

were presented[69]











Introduction

- 17 -






while







shown in detail















State of

Development


Introduction

- 18 -






and bis-stannylenes

















Introduction

- 19 -



prepared[74]






donor groups[72 76]
















Introduction

- 20 -


have received more






Motivation

- 21 -

2 MOTIVATION


























Motivation

- 22 -












- 23 -







and

(nacnac)GeCl3 2[82]




germanium derivates




derivative 3[83]




(nacnac)Ge-NH-



spectroscopy (1H


analyses



- 24 -












1H- and














but









- 25 -














35728(7) N1-C4 1382(3) C1-C2 1516(3) C2-C3 1411(3) C3-C4 1371(3)

C4-C5 1508(3) C2-Ge1-N1 843(1) C4-N1-Ge1 1130(1) C3-C2-C1 1202(2)

C3-C2-Ge1 1116(2) C1-C2-Ge1 1281(2) C4-C3-C2 1174(2) C3-C4-N1

1135(2) C3-C4-C5 1254(2)






- 26 -












1905(2) N1-C2 1329(3) N2-C4 1332(3) C1-C2 1518(3) C2-C3 1394(3)

C3-C4 1394(3) C4-C5 1512(3) N3-Ge1-N1 9720(8) N3-Ge1-N2 8876(9)


1227(2) C4-C3-C2 1269(3) N2-C4-C3 1239(3)


- 27 -























- 28 -








have been


species 5[83]











have been











- 29 -




and longer
















Ge2rsquo 1184(3) N2-C4-C3 1220(3)


cluster 5 The




- 30 -






cluster






- 31 -








compounds[93]







correlation[96]


The


approximation)[98]


potential



IGLO program[99]


theory[100]

The B3LYP[96a 101]


quality were









- 32 -































- 33 -














σ-character






150 pm abovea)


200 pm abovea)






a)



- 34 -


ring)
























- 35 -








(I27


I bonds










13C









- 36 -








ppm in the 119







The new GeI-Ge



I example Their







I


(257-








- 37 -

















Ge2 2549(1) Ge1-N1 2015(4) Ge1-N2 2038(4) Ge2-N3 1951(4) Ge2-C31

1903(5) N1-Ge1-N2 8867(15) N1-Ge1-Ge2 10430(11) N2-Ge1-Ge2


- 38 -

10149(12) C31-Ge2-N3 8447(19) C31-Ge2-Ge1 11890(15) N3-Ge2-Ge1


N3 1964(2) Ge1-C31 1915(3) N2-Sn1-N1 8288(8) N2-Sn1-Ge1 9542(5)


Ge1-Sn1 10200(6)


















- 39 -


I dimers






- 1206

LUMO

- 3911

HOMO

- 1138

LUMO

- 4024

HOMO

E [eV]

6a 8a

- 1206

LUMO

- 3911

HOMO

- 1138

LUMO

- 4024

HOMO

E [eV]

6a 8a















- 40 -







products[81-83 109]





benzenamine 9[111]




or (Z)-N-isopropyl








- 41 -

Et2O - 78degCnBuLi

Et2O - 78degCN

Dip

9

N

Dip

10

Li

N

Ph Dip

Cl

11

12

N

NH

Ph

Dip

Dip

Et2O - 78degC

N

Ph iPr

Cl

19

20

NH

N

Ph

Dip

iPr













respectively








- 42 -

N1C1

C2

C3 N2

Ph Dip

Dip

N1C1

C2

C3 N2

Ph iPr

Dip

1356

1386

1445

1309

1377

1360

1305

1452

12 20

HH





C13 14349(18) C1-C2 13769(19) C1-C4 15136(18) N2-C3 13046(16) N2-

C25 14297(17) C2-C3 14515(18) C2-C7 15257(18) N1-C1-C2 12221(12)

C1-C2-C3 12230(12) N2-C3-C2 12212(12) For 20 N1-C1 1309(2) N1-C17

1418(2) C1-C2 1445(2) C1-C4 1522(2) N2-C3 1356(2) N2-C14 1461(2)

C2-C3 1386(2) C2-C7 1524(2) C3-C8 1495(2) N1-C1-C2 12080(15) C1-

C2-C3 12151(15) N2-C3-C2 12288(15)






complex[27]



- 43 -























- 44 -



















published in 2006




22956(7) N1-C1 1342(3) N1-C14 1458(3) C1-C2 1397(3) C1-C8 1502(3)

N2-C3 1333(3) N2-C26 1463(2) C2-C3 1415(3) C2-C7 1522(3) C3-C4


- 45 -

1509(3) C4-C5 1522(3) N1-Ge1-N2 9123(7) N1-Ge1-Cl1 9560(5) N2-Ge1-

Cl1 9392(5) C1-N1-Ge1 12568(13) N1-C1-C2 12352(17) C1-C2-C3

12503(19) N2-C3-C2 12440(18) C3-N2-Ge1 12515(13)




N1-C8 1442(4) N2-C1 1408(4) N2-C20 1454(4) C1-C2 1359(4) C2-C3

1461(4) C1-C32 1498(4) C2-C7 1525(4) C3-C4 1360(4) N1-Ge1-N2

9509(11) C3-N1-Ge1 300(2) N1-C3-C2 1176(3) C1-C2-C3 1267(3) C2-C1-

N2 1241(3) C1-N2-Ge1 1259(2)











- 46 -











The 1H- and









154 ppm)[114]





and 3308 cmndash1


)[115]



- 47 -

= 3643 cmndash1




)[114]









due to the





[114]




N2 2017(2) Ge1-N3 1829(3) N1-C1 1349(4) C1-C2 1395(4) N2-C3

1336(4) C2-C3 1417(4) C3-C4 1509(4) N3-Ge1-N2 9503(11) N3-Ge1-N1

9709(13) N2-Ge1-N1 8932(10) C1-N1-Ge1 1253(2) C3-N2-Ge1 1247(2)

For 18 Ge1-O1 18249(18) Ge1-N2 20054(17) Ge1-N1 20071(16) N1-C1


- 48 -

1340(3) C1-C2 1402(3) N2-C3 1331(3) C2-C3 1419(3) C3-C4 1509(3)


12597(14) C3-N2-Ge1 12515(14)
















- 49 -









23 respectively














In compound 23 GeIV



center are





of the GeIV



- 50 -










Ge1-O1 18265(12) Ge1-N1 20908(15) O1-C6 1418(2) N1-C1 1284(2) N2-

C7 1272(2) C1-C6 1525(2) C6-C7 1539(2) Cl1-Ge1-O1 9789(4) Cl1-Ge1-

N1 9422(4) O1-Ge1-N1 8158(6) Ge1-N1-C1 11291(12) N1-C1-C6

11484(16) C1-C6-O1 10975(14) C6-O1-Ge1 11838(10) N2-C7-C6

11778(17) For 23 Ge1-Cl1 21339(7) Ge1-Cl2 21375(9) Ge1-N1 1798(2)

Ge1-N2 1788(2) N1-C1 1430(3) C1-C2 1339(4) C2-C3 1486(4) C3-C4

1326(4) N2-C3 1441(3) N2-Ge1-N1 10554(10) N2-Ge1-Cl1 11208(7) N1-


10276(3) C1-C2-C3 1266(2) C4-C3-N2 1209(2) C2-C4-C3 1208(3)





- 51 -







IIL [E = Si Ge Sn X











(aLSi-O-Si

aL

aL = PhC(


silylene I24[37]

(aLSi-Si




in








- 52 -





in 53 yield




in 76 yield The





tBu groups at δ =



Si-NMR spectrum of


- 53 -








aLSiO

iPr) (δ = -

135 ppm)[31b]

respectively


















package[101c 119]






The


- 54 -



(Figure 313)




20349(16) Cl2-Si2 22017(11) Si2-O1 1581(8) Si2-N3 1798(2) Si2-N4

1968(2) Si1-O1 1562(8) Si1-N2 1750(10) Si1-N1 1994(6) Si1-O1-Si2

1680(6)




1652(2) Si1-N1 1896(3) Si1-N2 1902(3) Si2-N3 1888(2) Si2-N4 1908(3)


N3 10196(11) O1-Si2-N4 10481(12) N1-Si1-N2 6815(10) N3-Si2-N4

6855(11)


- 55 -








29[32a]








- 56 -



















2216(2) pm][120]


(21395(8) pm)[121]









(2130-2146 pm)[121]





- 57 -

29

[Si][Si]

O

Ni

[Si] [Si]

Ni

CO CO

[Si] [Si]

Ni

N N tButBu

Si

N N DipDip

Si

[Si] = [Si] =

29a 29b

2207 2216

2191 2197689deg

934deg

1084deg 1019deg

1708 1701

2139 2139





Si1-N1 18929(19) Si1-N2 1875(2) Si2-O1 17081(17) Si2-N3 18776(19)


6941(9) N3-Si2-N4 6954(8)







- 58 -


Phosphasilene













oligomerize[126c]















- 59 -


aLSiCl



aL) 31






was easily


26[31a]





The 29





[31b] One





ppm)[31b]


- 60 -







aLSi-P




iPr2 derivative

[31b] The Si1-P1


pm) in the aLSi-P



subunit






- 61 -


10854(8)












72 yield





tBu






P-NMR spectrum



- 62 -








Phosphasilene[128]





(tBu3Si)2SiSi(Si














N2-Si1-N1 7078(11) P1-Si1-P1rsquo 10766(4)


- 63 -



















aLSiCl (1870(2) pm and 1917(2) pm)





- 64 -


















silylene 30 (0920)




- 65 -




























The


- 66 -




(Scheme 327)




















- 67 -





(Scheme 329) The



Si-N






(right)




N1 1832(7) Si1-N2 1827(7) Si1-N3 1705(7) Si2-N3 1780(7) Si3-N3



1248(4) Si2-N3-Si3 1179(4)


- 68 -















I58[61]

and

I64[65]










- 69 -












compound 35[33b]



13C-

and 29









- 70 -


singlet in the 29



tBu

iPr)

[31b]






31G(d)][101c 119]











(R = tBu

iPr)



- 71 -






by theoretical

calculation






O2-C3 13028


complex 36






36[33b]


(Scheme 333)


- 72 -













IV atom Si1 and the









complex[72b 77 135]




- 73 -


-Pd













23038(11) Si1-O1 1694(3) Si1-N1 1789(4) Si2-O2 1675(3) Si2-N5 1862(3)



Si2Si1

C1

Pd

Si3

213 pm

233 pm236 pm

230 pm

O1 O2


- 74 -

7861(11) Si2-Pd1-C1 7681(11) Si3-Pd1-C1 16783(12)


tBu groups









The 29



complexes[71 137]





The



)[135c 135f 136a]









335


- 75 -
















minus1


donor than PIII





minus1


- 76 -



and the first bis-






aLSi-Fc-Si


aLGe-Fc-Ge



PhD thesis[33a]









quantitatively














- 77 -






Si-NMR spectrum










The GeII centers






tBuC(N-Dip)2)




bidentate ligand


- 78 -




1979(9) Ge(2)-C(7) 1983(11) Ge(1)-N(1) 2027(8) Ge(1)-N(2) 2006(8)

Ge(2)-N(3) 2022(7) Ge(2)-N(4) 2037(7) C(1)-Ge(1)-N(2) 983(3) C(1)-Ge(1)-

N(1) 955(3) N(2)-Ge(1)-N(1) 653(3) C(7)-Ge(2)-N(3) 953(4) C(7)-Ge(2)-


Ge2-C8 19774(19) Ge1-N1 20261(16) Ge1-N2 20247(17) Ge2-N3

20402(15) Ge2-N4 20162(16) C1-Ge1-N1 9662(7) C1-Ge1-N2 9445(7) N1-


6459(6)




(Figure 323)


- 79 -







ferrocene molecules

6 9 0 6 9 5 7 0 0 7 0 5 7 1 0 7 1 5 7 2 0

m z

0

1 0

2 0

3 0

4 0

5 0

6 0

7 0

8 0

9 0

1 0 0

0

1 0

2 0

3 0

4 0

5 0

6 0

7 0

8 0

9 0

1 0 0

Re

lative

Abu

nda

nce

7 0 3 3 2 9

7 0 4 3 3 2

7 0 5 3 3 47 0 1 3 3 4

7 0 6 3 2 96 9 0 2 4 9 6 9 5 2 2 5 7 1 7 3 4 57 1 0 4 7 3

7 0 3 3 3 1

7 0 4 3 3 4

7 0 5 3 3 87 0 1 3 3 6

7 0 6 3 3 17 1 0 3 3 5

N L 3 1 3 E 7


N L 4 9 7 E 5


p a C hrg 1





- 80 -


recently[139]






transition-metals




0[32a


complex I65-Mo[66b]



[140] was





I

complex 41[33a]


42[33a]




- 81 -











42 δ = 699 737 and 891 ppm) In the 29













complex 41a[141]



[142] (21348(5) pm)


[143] (2228(2) pm) in


[141] (22060(6) and 22017(6) pm)






- 82 -





21252(14) Co1-Si2 21200(14) Si1-C6 1894(5) Si2-C11 1887(5) Si1-N1


9389(5) N1-Si1-N2 6847(15) N3-Si2-N4 6866(16) C6-Si1-Co1 13254(14)



- 83 -

C11 1961(4) Ge1-N1 2020(3) Ge1-N2 2031(3) Ge2-N3 2041(3) Ge2-N4

2029(3) Ge1-Co1-Ge2 9279(2) N1-Ge1-N2 6490(11) N3-Ge2-N4 6485(11)

C6-Ge1-Co1 13280(10) C11-Ge2-Co1 13140(10)



(2262(1) pm) and


4-((


and 25036(3) pm)[90d]


















- 84 -


tBu groups at δ =





of 41 In the 13






(ν = 1968 cmminus1

)[141]










tBu groups at δ =



Si-



- 85 -



C-



tBuO)SirarrFe(CO)4





)[71]
















2)-C(sp

3) coupling




- 86 -




expected[148]




Thus the catalytic


(Scheme 342)








- 87 -














- 88 -














Summary

- 89 -









in 33 yield








with KC8


in very low yield


dianion (CBD2-


core

Summary

- 90 -



and





in










Summary

- 91 -








was obtained by








in high yield










activation

Summary

- 92 -














[32a]



Summary

- 93 -







silylene 30[128]




product 31[128]










Summary

- 94 -









by 13-dilithium



as orange




SiIV




Summary

- 95 -











furnished





CoI complex 41


I complex 42

[33a]


Summary

- 96 -



are not shown












2)-C(sp

3)

cross-coupling[147]



Summary

- 97 -


probed[148-150]






- 98 -


51 General section




















dichloromethane





- 99 -









1H 400 MHz

13C


Si-NMR spectra were



The 1H and

13C








119Sn

1H external SnMe4








)












- 100 -






peak)























- 101 -










tBu [152]



9 (C5H10)C=N-Dip [111] 39 aLGeCl [41]



- 102 -











(030 g 083 mmol 33)





1H NMR (40013 MHz THF-D8 298K) δ = 108 (d

3JHH = 7 Hz 6 H




13C





378 Found C 5764 H 694 N 367




- 103 -

mmol 31)

NHN

GeN

Dip

DipDip

C41H59GeN3 MW 66657



1H NMR (40013 MHz C6D6 298K) δ = 091 (d

3JHH = 68 Hz 6 H


3JHH =





13C




C NCMe)

EI-MS mz () 6674 (03 [M]+) 4912 (100 [M -

iPr2C6H3NH]

+)


C 7354 H 868 N 613














- 104 -






C66H100Ge4K2N4O2 MW 135028


Found C 7821 H 999 N 281


C46H65Ge2N3 MW 80531








017 mmol 66)




- 105 -

1H NMR (40013 MHz C6D6 298K) δ = 107 (d

3JHH = 7 Hz 12 H


3JHH = 7




3JHH = 7 Hz 2 H



arom H)

13C






NCMe)





C 6884 H 800 N 516










- 106 -



dark red crystals



1H NMR (40013 MHz C6D6 298K) δ = 085 (d

3JHH = 7 Hz 6 H


3JHH = 7


3JHH = 7 Hz 6 H CHMe2) 129 (d




3JHH



721 (m 9 H arom H)

13C






NCMe)

119Sn NMR

(C6D6) δ = -197

UV-vis λ [nm] = 314 (15000) 363 (14500) 541 (2800)




Found C 6444 H 764 N 477


- 107 -


C37H48N2 MW 52079














1H NMR (40013 MHz CDCl3 298K) δ = 117 (d

3JHH = 7 Hz 6 H


3JHH = 7




arom H)

13C





CN) 1658 (Ph-CN)



8518 H 927 N 547


- 108 -


N

N

Ph

Dip

Dip

Cl

Ge












1H NMR (40013 MHz C6D6 298K) δ = 097 (d

3JHH = 7 Hz 3 H


3JHH = 7

Hz 3 H CHMe2) 121-127 (m 9 H CHMe2) 128-139 (m




3JHH = 7 Hz 1 H



13C





295 (Cy-CH2) 315 (Cy-CH2) 1089 (Cy-CCN) 1234-1476

(arom C) 1651 (Cy-CN) 1688 (Ph-CN)



Found C 7073 H 762 N 457


- 109 -


C37H46GeN2 MW 59142


ylidene 15[113]









1H NMR (40013 MHz C6D6 298K) δ = 115 (d

3JHH = 7 Hz 6 H


3JHH = 7




3JHH =

44 Hz 1 H C=CH) 675- 725 (m 11 H arom H)

13C




1117 (Cy-CCN) 1236-1431 (arom C) 1473 1474 (Cy-CN

Ph-CN)

IR (KBr cm-1

) 704 (s) 787 (s) 939 (m) 1104 (s) 1135 (s) 1204 (s) 1248 (s)

1296 (s) 1322 (s) 1365 (s) 1439 (s) 1461 (s) 1535 (m) 1600

(s) 2822 (m) 2865 (s) 2922 (s) 2957 (w) 3022 (w) 3061 (m)



C 7495 H 800 N 484


- 110 -


C37H49GeN3 MW 60845








1H NMR (40013 MHz C6D6 298K) δ = 106 (d

3JHH = 7 Hz 3 H



154 (s 2 H NH2) 200-213 (m 4 H Cy-CH2) 346 (sept


3JHH = 7 Hz 1 H



13C





293 (Cy-CH2) 315 (Cy-CH2) 1023 (Cy-CCN) 1234-1462

(arom C) 1643 (Cy-CN) 1669 (Ph-CN)

IR (KBr cm-1

) 561 (s) 704 (s) 752 (s) 796 (s) 839 (m) 922 (s) 1096 (s)

1143 (s) 1174 (s) 1252 (s) 1304 (s) 1360 (s) 1430 (s) 1543

(s) 2865 (m) 2961 (s) 3021 (w) 3048 (m) 3343 (w) 3430

(w)


C 7272 H 810 N 683


- 111 -










1H NMR (40013 MHz C6D6 298K) δ = 111 (d

3JHH = 7 Hz 3 H



166 (s 1 H OH) 195-221 (m 4 H Cy-CH2) 335 (sept


3JHH = 7 Hz 1 H



13C





291 (Cy-CH2) 314 (Cy-CH2) 1028 (Cy-CCN) 1233-1464

(arom C) 1647 (Cy-CN) 1666 (Ph-CN)

IR(KBr cm-1

) 561 (s) 713 (s) 743 (s) 770 (s) 791 (s) 839 (s) 926 (m)

1056 (m) 1104 (s) 1148 (s) 1170 (s) 1257 (s) 1313 (s) 1339

(s) 1365 (s) 1430 (s) 1470 (s) 1539 (s) 2861 (s) 2961 (s)

3018 (w) 3057 (m) 3643 (m)




- 112 -

Found C 7300 H 786 N 464


C28H38N2 MW 40230













1H NMR (40013 MHz CDCl3 298K) δ = 109 (d

3JHH = 7 Hz 6 H


3JHH = 7




1203 (d 3JHH = 7 Hz 1 H NH)

13C




(Cy-CCN) 1226 1228 1275 1282 1284 1371 1389

1453 (arom C) 1576 (Cy-CN) 1673 (PhCN)



- 113 -


8270 H 977 N 679













1H NMR (40013 MHz C6D6 298K) δ = 106 (d

3JHH = 7 Hz 3 H


3JHH = 7






3JHH = 7 Hz


1 H arom H) 705-724 (m 7 H arom H)

13C





- 114 -

293 (Cy-CH2) 312 (Cy-CH2) 537 (CHMe2) 1068 (Cy-

CCN) 1239 1250 1267 1271 1288 1294 1388 1410

1446 1469 (arom C) 1620 (Cy-CN) 1654 (Ph-CN)


Found C 6426 H 725 N 551










287 mmol 57 )



1H NMR (40013 MHz C6D6 298K) δ = 113 (d

3JHH = 7 Hz 6 H


3JHH = 7




3JHH =

42 Hz 1 H C=CH) 701-726 (m 8 H arom H)

13C


CH2) 247 (CHMe2) 254 (Cy-CH2) 257 (CHMe2) 286


- 115 -


1125 (Cy-CCN) 1248 1287 1296 1354 1391 1411

1421 1490 (arom C) 1682 (Cy-CN) 1709 (Ph-CN)


Found C 6203 H 517 N 679




tBu













(s 2 H SiHCl) 733- 746 (m 10 H arom H)

13C


1276 1285 1297 1337 (arom C) 1711 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = -1110

IR(KBr cm-1

) 606 (s) 658 (m) 711 (s) 733 (s) 760 (s) 789 (s) 934 (s)

1068 (s) 1200 (s) 1269 (s) 1378 (s) 1486 (s) 1550 (s) 1566

(s) 1612 (s) 1783 (w) 1826 (w) 1950 (w) 1969 (w) 2000


- 116 -

(w) 2135 (s) 2188 (s) 2909 (s) 2934 (s) 2971 (s) 3232 (m)



Found C 5971 H 797 N 913


C30H46N4OSi2 MW 53488










731(m 10 H arom H)

13C


1277 1291 1299 1349 (arom C) 1623 (NCN)

29Si

1H NMR (7949 MHz C6D6 298K) δ = -161

IR(KBr cm-1

) 608 (s) 709 (s) 746 (s) 790 (s) 892 (m) 972 (s) 1032 (m)

1070 (m) 1208 (s) 1268 (m) 1359 (s) 1412 (s) 1446 (s)

1476 (s) 1577 (m) 1648 (m) 1778 (w) 1826 (w) 1899 (w)

1970 (w) 2248 (w) 2867 (s) 2902 (s) 2928 (s) 2964 (s)

3065 (m)


- 117 -



Found C 6688 H 857 N 1046












(m 4 H CH2) 295 (m 4 H CH2) 504 (s 4 H =CH) 686-

707 (m 10 H arom H)

13C


(CMe3) 760 (=CH) 1277 1293 1296 1335 (arom C)

1690 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = 328

IR(KBr cm-1

) 607 (s) 644 (s) 698 (s) 750 (s) 792 (s) 925 (m) 1021 (m)

1075 (s) 1209 (s) 1267 (s) 1320 (m) 1361 (s) 1407 (s)

1444 (s) 1475 (s) 1578 (m) 1647 (m) 1775 (w) 1823 (w)


- 118 -

1902 (w) 1962 (w) 2280 (w) 2791 (s) 2855 (s) 2913 (s)

2975 (s) 3023 (m) 3063 (w)



Found C 6387 H 837 N 805


C21H41N2PSi3 MW 43679


(302 mg 102





085 mmol 83)



1H NMR (40013 MHz C6D6 298K) δ = 058 (d

3JP-H = 44 Hz 18 H


734-741 (m 3 H arom H)

13C

1H NMR (10061 MHz C6D6 298K) δ = 44 (d

3JC-P = 100 Hz


1292 1293 1344 (arom C) 1572 (d 3JC-P = 95 Hz

NCN)

29Si

1H NMR (7949 MHz C6D6 298K) δ = 31 (d

1JSi-P = 229 Hz


31P NMR (81012 MHz C6D6 298K) δ = - 2110


- 119 -



C30H46N4P2Si2 MW 58083





mg 025 mmol 72)




733 (m 10 H arom H)

13C


(CMe3) 1256 1276 1294 1359 (arom C) 1710 (NCN)

29Si

1H NMR (7949 MHz THF-D8 298K) δ = 267 (t

1JSi-P = 998 Hz)

31P NMR (81012 MHz THF-D8 298K) δ = - 1649


5802361


- 120 -




(336 mg 114










689 Found C 4195 H 701 N 706


C44H66N4O2Si2 MW 73919









- 121 -





174 (s 18 H ArC(CH3)3) 693 - 713 (m 8 H arom H) 754


13C


(NC(CH3)3) 350 (ArC(CH3)3) 530 (NC(CH3)3) 1096

1243 1276 1295 1297 1313 1341 1552 (arom C)

1636 (NCN)

29Si

1H NMR (7949 MHz C6D6 298K) δ = -240


Found C 7075 H 930 N 756


C88H132N8O4PdSi4 MW 158480








- 122 -






(s 9 H C(CH3)3) 114 (s 9 H C(CH3)3) 116 (s 9 H

C(CH3)3) 131 (s 9 H C(CH3)3) 139 (s 9 H C(CH3)3)155

(s 9 H C(CH3)3) 168 (s 9 H C(CH3)3) 177 (s 9 H

C(CH3)3) 180 (s 9 H C(CH3)3) 185 (s 9 H C(CH3)3) 212

(s 9 H C(CH3)3) 659 (s 1 H SiH) 686- 789 (m 22 H


13C

1H NMR (10061 MHz C6D6 298K) δ = 309 (C(CH3)3) 311

(C(CH3)3) 314 (C(CH3)3) 316 (C(CH3)3) 318 (C(CH3)3)

319 (C(CH3)3) 320 (C(CH3)3) 322 (C(CH3)3) 328

(C(CH3)3) 332 (C(CH3)3) 333 (C(CH3)3) 343 (C(CH3)3)

349 350 351 357 526 527 537 539 540 541 542

561 1112 1225 1236 1243 1256 1258 1271 1285

1287 1289 1291 1293 1294 1302 1303 1318 1323

1324 1326 1340 1342 1378 1380 1381 1409 1430

1533 1559 1585 1613 1622 1654 1731 1742

29Si


658 (LSiPd)

IR(KBr cm-1

) 623 (m) 706 (m) 764 (m) 860 (m) 1056 (m) 1108 (m) 1206

(m) 1272 (m) 1365 (m) 1418 (s) 1446 (m) 1476 (m) 1446

(m) 1476 (m) 1495 (m) 1591 (m) 2135 (w) 2875(m) 2906

(s) 2964 (s) 3061 (w)


707 Found C 6616 H 875 N 676


- 123 -















451 (t 3JHH = 15 Hz 4 H FeCH) 472 (t

3JHH = 15 Hz 4 H

FeCH) 692- 707 (m 10 H arom H)

13C



1294 1305 1349 (arom C) 1604 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = 433



Found C 6803 H 767 N 778


- 124 -















(t 3JHH = 16 Hz 4 H FeCH) 471 (t

3JHH = 16 Hz 4 H


H)

13C



1290 1302 1369 (arom C) 1659 (NCN)


C 6655 H 701 N 707


- 125 -


tBu

N

N

tBu

PhSi

tBu

N

N

tBu

Ph Si

Co

Fe













440 (t 3JHH = 16 Hz 4 H FeCH) 461 (t

3JHH = 16 Hz 4 H


692- 696 (m 6 H arom H) 720- 723 (m 2 H arom H)

13C



(SiC) 1291 1297 1300 1343 (arom C) 1673 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = 820



Found C 6612 H 724 N 686


- 126 -


tBu

N

N

tBu

PhGe

tBu

N

N

tBu

Ph Ge

Co

Fe













438 (t 3JHH = 15 Hz 4 H FeCH) 459 (t

3JHH = 15 Hz 4 H


695- 698 (m 6 H arom H) 714- 718 (m 2 H arom H)

13C



(GeC) 1287 1296 1300 1361(arom C) 1680 (NCN)


Found C 5942 H 664 N 590


- 127 -











461 (m 4 H FeCH) 476 (m 4 H FeCH) 523 (s 10 H

CoCH) 683- 695 (m 6 H arom H) 702- 706 (m 2 H

arom H) 745- 748 (m 2 H arom H)

13C



(CoCH) 1287 1296 1300 1324 (arom C) 1687 (NCN)

2078 (br CO)

29Si

1H NMR (7949 MHz C6D6 298K) δ = 857

IR(KBr cm-1

) 500 (m) 539 (w) 564 (m) 628 (s) 703 (m) 757 (s) 792 (m)

825 (w) 1028 (m) 1081 (w) 1146 (m) 1199 (s) 1275 (m)

1360 (m) 1388 (m) 1417 (s) 1438 (w) 1474 (m) 1520 (s)

1641 (s) 1888 (s) 2869 (s) 2901 (m) 2926 (m) 2965 (s)

1520 (s) 3097 (w)



- 128 -

556 Found C 6287 H 630 N 571


C48H54Fe3N4O8Si2 MW 103867










H) 736- 739 (m 2 H arom H)

13C



1287 1303 1308 (arom C) 1704 (NCN) 2169 (CO)

29Si

1H NMR (7949 MHz C6D6 298K) δ = 1050

IR(KBr cm-1

) 630 (s) 765 (w) 1028 (m) 1035 (m) 1200 (m) 1370 (w)

1400 (m) 1474 (w) 1609 (w) 1648 (w) 1900 (s) 1948 (s)

1996(w) 2026 (s) 2865 (w) 2930 (m) 2965 (m)


539 Found C 5623 H 517 N 566

References

- 129 -

6 REFERENCES



353


3877












2010 16 436


1955 77 884











Chem Int Ed 2003 42 2222




Chem Soc 1994 116 3667







References

- 130 -










5683













11366


Science 2008 321 1069




12315











9701




References

- 131 -

2008 47 1650






121 347







Int Ed 2011 50 5374


1991 1302


2004 630 2090



4130


1994 33 1156


Int Ed 1997 36 261


Inorg Chem 1997 36 5202



2008 130 12268



127 17530











References

- 132 -


















2012 51 399


5058















2011 44 588









References

- 133 -










20 1190



Allg Chem 2001 627 836




Soc 1996 118 10457





3655






Soc 2011 133 5103



Soc 1996 118 6317


Chem Rev 2005 105 3842










Phys 2000 2 2137

References

- 134 -



Phys Rev 1988 37 785









Chem Soc 2006 128 1023










2005 127 3516


2004 43 1419



2343




2003 pp 2217













References

- 135 -



CT 2004
























2868

















References

- 136 -












Chem Int Ed 2007 46 4141



2009 82 793







Chem 2011 50 8502




1804

















7162

References

- 137 -




Appendix

- 138 -

7 APPENDIX

71 Abbreviations



mmol millimole(ar)





















Et ethyl t triplet







IR infrared

K Kelvin


functions aL PhC(

tBuN)2








Appendix

- 139 -

GeN

N

GeN

Dip

Dip

DipCl

N

SnN

Dip

Dip

GeNN

SnN

Dip

DipDip

N

Dip

6 7


1 2 3 4

5 8 9

10 11 12 13 14

15 16 17 18

19 20 21 22

Appendix

- 140 -

23 24 25 26

27 28 29

30 31 32 33

34 35 36

tBu

N

N

tBu

Ph

Si

Cl

37 38 39 40

Appendix

- 141 -

tBu

N

N

tBu

PhSi

tBu

N

N

tBu

Ph Si

Co

Fe

41 42 43

44 45 46

47a 47b 48a 48b

Appendix

- 142 -



Compound 3 4 5

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C50 H88 Ge2 K2 N2 O4

100460

150(2)

71073

Triclinic

P-1

106989(7) pm

114137(7) pm

122625(8) pm

74158(6) deg

76395(6) deg

83400(5) deg

139807(16)

1

1193

1263

536

028 x 02 x 018

326 to 2500deg

-12lt=hlt=12

-13lt=klt=13

-14lt=llt=14

12268

4910 [R(int) = 00358]

996


100000 and 094847


4910 0 281

0940

R1 = 00328 wR2 = 00638

R1 = 00538 wR2 = 00666

0456 and -0223

C41 H5 Ge N3

66650

150(2)

71073

Triclinic

P-1

91129(6) pm

113531(7) pm

190282(10) pm

100360(5) deg

101854(5) deg

98627(5) deg

185918(19)

2

1191

0855

716

039 x 012 x 007

297 to 2500deg

-10lt=hlt=10

-13lt=klt=13

-22lt=llt=22

14570

6543 [R(int) = 00560]

998


0943 and 0777


6543 0 420

0785

R1 = 00399 wR2 = 00513

R1 = 00853 wR2 = 00566

0577 and -0317

C66 H102 Ge4 K2 N4 O2

135208

150(2)

71073

Monoclinic

P21n

12370(3) pm

148433(14) pm

188725(19) pm

90059(8)deg

96311(14)deg

90082(13)deg

34442(10)

2

1304

1892

1416

030 x 025 x 015

292 to 2500deg

-14lt=hlt=14

-15lt=klt=17

-14lt=llt=22

17371

6032 [R(int) = 00487]

995

Analytical

0807 and 0584


6032 2 364

0911

R1 = 00424 wR2 = 00801

R1 = 00874 wR2 = 00885

0497 and -0457

Appendix

- 143 -


Compound 6 8 12

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C46 H65 Ge2 N3

80519

150(2)

71073

Monoclinic

C2c

44536(2) pm

98204(5) pm

218135(10) pm

90deg

116030(4)deg

90deg

85727(7)

8

1248

1436

3408

038 x 024 x 010

305 to 2500deg

-49lt=hlt=52

-10lt=klt=11

-24lt=llt=25

20162

7493 [R(int) = 00954]

992


100000 and 074676


7493 0 476

0917

R1 = 00559 wR2 = 00778

R1 = 01461 wR2 = 00966

0590 and -0578

C46 H65 Ge N3 Sn

85129

150(2)

71073

Triclinic

P-1

867780(10) pm

120514(4) pm

210797(6) pm

96333(2)deg

97393(2)deg

99141(2)deg

213908(10)

2

1322

1320

888

016 x 014 x 012

295 to 2500deg

-10lt=hlt=10

-14lt=klt=14

-25lt=llt=25

16936

7496 [R(int) = 00251]

994


100000 and 099037


7496 0 495

1001

R1 = 00309 wR2 = 00706

R1 = 00437 wR2 = 00733

1468 and -0424

C37 H48 N2

52077

150(2)

71073

Triclinic

P-1

108485(5) pm

127284(7) pm

132348(4) pm

65748(4)deg

86290(3)deg

71699(5)deg

157759(12)

2

1096

0063

568

029 x 022 x 018

298 to 2500deg

-11lt=hlt=12

-15lt=klt=15

-15lt=llt=15

13428

5541 [R(int) = 00203]

998

None

09888 and 09820


5541 0 364

1029

R1 = 00439 wR2 = 00900

R1 = 00633 wR2 = 00963

0188 and -0193

Appendix

- 144 -


Compound 14 16 17

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C37 H46 Cl Ge N2

62680

150(2)

71073

Monoclinic

P21c

117621(2) pm

175495(4) pm

166051(3) pm

90deg

107053(2)deg

90deg

327691(11)

4

1270

1044

1324

040 x 032 x 022

342 to 2500deg

-13lt=hlt=13

-19lt=klt=20

-19lt=llt=18

16923

5742 [R(int) = 00250]

997


100000 and 082078


5742 0 378

1044

R1 = 00328 wR2 = 00709

R1 = 00496 wR2 = 00742

0736 and -0362

C37 H46 Ge N2

59135

150(2)

71073

Triclinic

P-1

108388(6) pm

127885(7) pm

132778(4) pm

66971(4)deg

85749(3)deg

71833(5)deg

160695(13)

2

1222

0980

628

029 x 015 x 007

307 to 2500deg

-12lt=hlt=12

-15lt=klt=15

-15lt=llt=15

13501

5636 [R(int) = 00366]

996


100000 and 092510


5636 0 369

1031

R1 = 00489 wR2 = 01180

R1 = 00691 wR2 = 01242

0539 and -0501

C37 H49 Ge N3

60838

150(2)

71073

Monoclinic

P21c

117714(4) pm

174309(6) pm

166868(6) pm

90deg

106866(4)deg

90deg

32766(2)

4

1233

0964

1296

030 x 023 x 019

342 to 2500deg

-8lt=hlt=13

-10lt=klt=20

-19lt=llt=16

12816

5749 [R(int) = 00325]

998


100000 and 095425


5749 0 378

1060

R1 = 00464 wR2 = 01084

R1 = 00699 wR2 = 01133

1717 and -0738

Appendix

- 145 -


Compound 18 20 22

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C37 H48 Ge N2 O

60936

150(2)

71073

Monoclinic

P21c

117560(3) pm

174116(5) pm

166421(4) pm

90deg

106992(3)deg

90deg

325778(15)

4

1242

0971

1296

031 x 014 x 005

343 to 2500deg

-13lt=hlt=13

-20lt=klt=20

-19lt=llt=19

23624

5720 [R(int) = 00371]

998


100000 and 083390


5720 0 379

1018

R1 = 00336 wR2 = 00752

R1 = 00516 wR2 = 00789

0521 and -0366

C28 H38 N2

40260

150(2)

71073

Monoclinic

P21c

94924(4) pm

256583(9) pm

107465(5) pm

90deg

110403(5)deg

90deg

245320(18)

4

1090

0063

880

017 x 015 x 013

343 to 2500deg

-11lt=hlt=10

-30lt=klt=27

-12lt=llt=11

8561

4313 [R(int) = 00209]

997


100000 and 099057


4313 0 281

1041

R1 = 00476 wR2 = 01015

R1 = 00771 wR2 = 01083

0253 and -0194

C28 H37 Cl Ge N2 O

52564

150(2)

71073

Triclinic

P-1

89021(3) pm

107319(4) pm

151176(6) pm

75734(4)deg

74781(3)deg

75311(3)deg

132282(8)

2

1320

1281

552

020 x 012 x 008

354 to 2500deg

-10lt=hlt=10

-12lt=klt=12

-15lt=llt=17

9246

4654 [R(int) = 00211]

997


100000 and 086160


4654 0 304

0946

R1 = 00274 wR2 = 00579

R1 = 00386 wR2 = 00597

0394 and -0264

Appendix

- 146 -


Compound 23 27 28

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C28 H36 Cl2 Ge N2

54408

150(2)

71073

Monoclinic

C2c

279616(13) pm

113538(3) pm

177729(7) pm

90deg

109718(5)deg

90deg

53115(4)

8

1361

1374

2272

021 x 017 x 015

332 to 2500deg

-25lt=hlt=33

-7lt=klt=13

-21lt=llt=20

10951

4663 [R(int) = 00459]

997


100000 and 091223


4663 0 304

0856

R1 = 00372 wR2 = 00584

R1 = 00684 wR2 = 00620

0589 and -0533


60780

150(2)

71073

Monoclinic

P21c

121593(5) pm

162045(6) pm

171248(7) pm

90deg

98177(4)deg

90deg

33399(2)

4

1209

0295

1304

030 x 015 x 005

335 to 2500deg

-14lt=hlt=13

-16lt=klt=19

-20lt=llt=20

23741

5865 [R(int) = 00491]

998


100000 and 086688


5865 172 490

1035

R1 = 00543 wR2 = 01080

R1 = 00905 wR2 = 01194

0310 and -0412

C30 H46 N4 O Si2

53489

150(2)

71073

Orthorhombic

Fdd2

31188(2) pm

39120(3) pm

102620(6) pm

90deg

90deg

90deg

125204(14)

16

1135

0141

4640

031 x 011 x 007

334 to 2500deg

-28lt=hlt=36

-46lt=klt=45

-12lt=llt=12

11517

4372 [R(int) = 00656]

997


100000 and 097469


4372 1 346

0897

R1 = 00488 wR2 = 00604

R1 = 00754 wR2 = 00650

0328 and -0229

Appendix

- 147 -


Compound 29 30 31

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C38 H58 N4 Ni O Si2

70177

150(2)

71073

Triclinic

P-1

98776(8) pm

129530(11) pm

155488(13) pm

81634(7)deg

83316(7)deg

82826(7)deg

19430(3)

2

1200

0594

756

020 x 009 x 007

330 to 2500deg

-11lt=hlt=11

-15lt=klt=13

-18lt=llt=18

14961

6828 [R(int) = 00414]

997


100000 and 091998


6828 0 474

0948

R1 = 00386 wR2 = 00807

R1 = 00605 wR2 = 00853

0407 and -0240

C21 H41 N2 P Si3

43680

173(2)

71073

Orthorhombic

Pbca

193556(7) pm

142399(4) pm

199777(6) pm

90deg

90deg

90deg

55063(3)

8

1054

0239

1904

039 x 036 x 016

351 to 2500deg

-13lt=hlt=23

-16lt=klt=16

-23lt=llt=22

19912

4836 [R(int) = 00961]

998


09627 and 09125


4836 18 287

0906

R1 = 00571 wR2 = 00889

R1 = 01270 wR2 = 01032

0316 and -0214

C44 H60 N4 P2 Si2

76308

173(2)

71073

Monoclinic

C2c

23841(3) pm

101993(12) pm

19369(2) pm

90deg

108346(12)deg

90deg

44703(9)

4

1134

0184

1640

076 x 057 x 055

353 to 2500deg

-28lt=hlt=28

-12lt=klt=12

-20lt=llt=23

16197

3927 [R(int) = 00447]

997


09053 and 08725


3927 0 251

1034

R1 = 00618 wR2 = 01393

R1 = 00843 wR2 = 01489

0721 and -0649

Appendix

- 148 -



Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)


140312

150(2)

71073

Triclinic

P-1

105159(4) pm

127622(6) pm

269391(12) pm

90310(4)deg

90855(3)deg

102927(3)deg

35232(3)

2

1323

1000

1456

013 x 012 x 009

336 to 2500deg

-12lt=hlt=12

-15lt=klt=15

-29lt=llt=32

25757

12396 [R(int) = 00546]

997


09154 and 08810


12396 536 816

2077

R1 = 01231 wR2 = 01906

R1 = 01495 wR2 = 01944

1510 and -4753

C91 H139 N8 O4 Pd Si4

162786

150(2)

71073

Triclinic

P-1

145970(8) pm

151441(15) pm

232982(16) pm

71358(8)deg

74666(5)deg

85365(6)deg

47063(6)

2

1149

0298

1750

019 x 013 x 011

327 to 2500deg

-17lt=hlt=17

-17lt=klt=18

-27lt=llt=27

41022

16531 [R(int) = 00735]

998


09679 and 09455


16531 284 1112

0908

R1 = 00558 wR2 = 01021

R1 = 01075 wR2 = 01128

0688 and -0448

C40 H54 Fe Ge2 N4

79190

150(2)

71073

Monoclinic

P21n

10532(3) pm

20258(5) pm

18990(5) pm

90deg

10542(3)deg

90deg

39060(19)

4

1347

1927

1648

012 x 008 x 005

322 to 2500deg

-6lt=hlt=12

-22lt=klt=24

-22lt=llt=21

16887

6870 [R(int) = 01353]

997


100000 and 073478


6870 213 498

1044

R1 = 00912 wR2 = 01786

R1 = 01680 wR2 = 02282

0570 and -1404

Appendix

- 149 -



Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C40 H54 Fe Ge2 N4

79190

150(2)

71073

Monoclinic

P21n

165582(11) pm

127695(7) pm

198175(12) pm

90deg

107428(7)deg

90deg

39979(4)

4

1316

1883

1648

012 x 011 x 009

337 to 2499deg

-16lt=hlt=19

-15lt=klt=15

-23lt=llt=23

29049

7015 [R(int) = 00329]

998


100000 and 052405


7015 0 436

1065

R1 = 00263 wR2 = 00574

R1 = 00318 wR2 = 00595

0357 and -0360


82692

150(2)

71073

Monoclinic

P21c

119176(7) pm

160794(9) pm

220424(13) pm

90deg

94402(5)deg

90deg

42115(4)

4

1304

0831

1752

015 x 013 x 007

323 to 2500deg

-14lt=hlt=14

-19lt=klt=17

-16lt=llt=26

17786

7404 [R(int) = 01111]

998


100000 and 075122


7404 0 490

1052

R1 = 00717 wR2 = 01045

R1 = 01208 wR2 = 01181

0467 and -0370


91592

150(2)

71073

Monoclinic

P21c

121662(3) pm

160596(3) pm

220073(5) pm

90deg

93549(2)deg

90deg

429163(16)

4

1418

2134

1896

015 x 011 x 008

336 to 2500deg

-14lt=hlt=14

-19lt=klt=19

-26lt=llt=26

33743

7539 [R(int) = 00521]

998


100000 and 068509


7539 0 521

1259

R1 = 00400 wR2 = 00965

R1 = 00536 wR2 = 01000

0376 and -0373

Appendix

- 150 -


following tables



2times10

3)


x y z U(eq)

N(1) 1159(1) 1176(1) 6836(1) 20(1)

C(1) 1706(2) 1650(1) 6995(1) 21(1)

N(2) -1293(2) 1547(1) 7057(1) 23(1)

C(2) 789(2) 2089(1) 7078(1) 20(1)

C(3) -626(2) 2021(1) 7158(1) 20(1)

C(4) 3331(2) 1741(1) 7112(2) 29(1)

C(5) 3920(2) 2283(1) 7590(2) 34(1)

C(6) 2795(2) 2681(1) 6772(2) 35(1)

C(7) 1375(2) 2643(1) 7102(2) 27(1)

C(8) -1522(2) 2482(1) 7295(2) 21(1)

C(9) -2759(2) 2643(1) 6227(2) 27(1)

C(10) -3571(2) 3077(1) 6331(2) 33(1)

C(11) -3169(2) 3358(1) 7498(2) 35(1)

C(12) -1948(2) 3199(1) 8573(2) 32(1)

C(13) -1133(2) 2765(1) 8467(2) 27(1)

C(14) -2537(2) 1417(1) 7503(2) 35(1)

C(15) -3250(3) 920(1) 6823(2) 61(1)

C(16) -1974(3) 1344(1) 9002(2) 65(1)

C(17) 2080(2) 741(1) 6834(2) 20(1)

C(18) 2353(2) 597(1) 5670(2) 23(1)

C(19) 3237(2) 160(1) 5724(2) 29(1)

C(20) 3821(2) -131(1) 6867(2) 32(1)

C(21) 3480(2) -1(1) 7977(2) 29(1)

C(22) 2598(2) 427(1) 7984(2) 23(1)

C(23) 2150(2) 562(1) 9174(2) 28(1)

C(24) 2101(2) 91(1) 10028(2) 39(1)

C(25) 3156(2) 987(1) 10029(2) 42(1)

C(26) 1602(2) 885(1) 4374(2) 29(1)

C(27) 2645(3) 974(1) 3586(2) 53(1)

C(28) 195(3) 588(1) 3539(2) 54(1)

Appendix

- 151 -


2times10

3)


x y z U(eq)

Ge(1) 4751(1) 5279(1) 3913(1) 24(1)

Cl(1) 4863(1) 7474(1) 3443(1) 35(1)

O(1) 2591(1) 5468(1) 4187(1) 20(1)

N(1) 4469(2) 5098(1) 2623(1) 17(1)

C(1) 3006(2) 5278(2) 2582(1) 16(1)

N(2) 1482(2) 7765(2) 2375(1) 20(1)

C(2) 2432(2) 5062(2) 1801(1) 21(1)

C(3) 1144(2) 4228(2) 2174(2) 31(1)

C(4) -158(2) 4793(2) 2933(2) 30(1)

C(5) 534(2) 4844(2) 3741(1) 21(1)

C(6) 1810(2) 5684(2) 3440(1) 17(1)

C(7) 1063(2) 7152(2) 3205(1) 18(1)

C(8) 820(2) 9172(2) 2096(1) 26(1)

C(9) 397(3) 9344(2) 1159(2) 40(1)

C(10) 2058(3) 9950(2) 2035(2) 43(1)

C(11) -95(2) 7719(2) 3998(1) 18(1)

C(12) 434(2) 8108(2) 4652(1) 22(1)

C(13) -648(2) 8637(2) 5376(1) 27(1)

C(14) -2259(2) 8769(2) 5459(2) 30(1)

C(15) -2795(2) 8370(2) 4815(2) 30(1)

C(16) -1724(2) 7845(2) 4085(1) 24(1)

C(17) 5786(2) 4690(2) 1889(1) 19(1)

C(18) 6546(2) 3361(2) 1997(1) 22(1)

C(19) 7868(2) 3005(2) 1310(2) 28(1)

C(20) 8423(2) 3902(2) 552(2) 29(1)

C(21) 7656(2) 5209(2) 464(1) 26(1)

C(22) 6329(2) 5635(2) 1128(1) 21(1)

C(23) 5549(2) 7085(2) 991(2) 26(1)

C(24) 6701(3) 7932(2) 989(2) 41(1)

C(25) 4931(3) 7520(2) 84(2) 40(1)

C(26) 6001(2) 2315(2) 2820(2) 27(1)

C(27) 5775(3) 1139(2) 2495(2) 40(1)

C(28) 7175(3) 1863(2) 3471(2) 38(1)

Appendix

- 152 -


2times10

3)


x y z U(eq)

Ge(1) 967(1) 7605(1) 1823(1) 18(1)

Cl(1) 1020(1) 9314(1) 2345(1) 29(1)

N(1) 1401(1) 6550(2) 2449(1) 19(1)

C(1) 1534(1) 5601(2) 2029(2) 16(1)

Cl(2) 198(1) 7116(1) 1640(1) 31(1)

N(2) 1101(1) 7630(2) 909(1) 15(1)

C(2) 1548(1) 5691(2) 1285(2) 15(1)

C(3) 1442(1) 6764(2) 777(2) 14(1)

C(4) 1615(1) 6867(2) 172(2) 19(1)

C(5) 1945(1) 5989(2) -42(2) 26(1)

C(6) 2098(1) 4966(2) 547(2) 22(1)

C(7) 1669(1) 4652(2) 844(2) 21(1)

C(8) 1625(1) 4444(2) 2470(2) 17(1)

C(9) 1229(1) 3875(2) 2611(2) 23(1)

C(10) 1291(1) 2785(2) 2983(2) 29(1)

C(11) 1764(2) 2263(3) 3232(2) 32(1)

C(12) 2169(1) 2832(3) 3121(2) 30(1)

C(13) 2101(1) 3920(2) 2737(2) 22(1)

C(14) 1621(1) 6630(2) 3327(2) 20(1)

C(15) 1219(1) 6848(3) 3699(2) 32(1)

C(16) 2052(1) 7524(2) 3583(2) 34(1)

C(17) 833(1) 8395(2) 248(2) 17(1)

C(18) 1019(1) 9542(2) 207(2) 19(1)

C(19) 745(1) 10248(3) -431(2) 29(1)

C(20) 315(1) 9844(3) -1011(2) 36(1)

C(21) 147(1) 8718(3) -973(2) 33(1)

C(22) 399(1) 7960(2) -350(2) 20(1)

C(23) 215(1) 6700(2) -377(2) 23(1)

C(24) 329(1) 6020(3) -1045(2) 34(1)

C(25) -341(1) 6612(3) -475(2) 31(1)

C(26) 1517(1) 10001(2) 789(2) 22(1)

C(27) 1914(1) 10083(3) 375(2) 32(1)

C(28) 1463(1) 11198(2) 1144(2) 36(1)

Appendix

- 153 -


2times10

3)


x y z U(eq)

Sn(1) 4689(1) 4918(1) 3222(1) 24(1)

Sn(2) 5822(1) 5994(1) 1674(1) 30(1)

Cl(1) 4488(3) 6215(2) 3883(1) 38(1)

Cl(2) 3266(2) 3378(2) 3638(1) 39(1)

Cl(3) 7188(2) 7769(2) 1449(1) 43(1)

Cl(4) 6104(3) 5090(3) 888(1) 57(1)

Si(1) 6825(2) 4259(2) 3587(1) 17(1)

Si(2) 8610(3) 6420(2) 3531(1) 28(1)

Si(3) 9814(2) 4466(2) 3664(1) 26(1)

Si(4) 3648(2) 6680(2) 1375(1) 21(1)

Si(5) 1981(3) 4463(2) 1299(1) 30(1)

Si(6) 649(3) 6348(2) 1247(1) 30(1)

N(1) 6586(7) 2924(5) 3299(3) 20(2)

N(2) 6484(6) 3264(5) 4080(3) 16(2)

N(3) 8389(7) 5001(5) 3582(3) 23(2)

N(4) 3751(7) 7937(6) 1722(3) 22(2)

N(5) 3959(8) 7800(6) 936(3) 27(2)

N(6) 2102(7) 5865(6) 1329(3) 24(2)

C(1) 6258(8) 2470(7) 3742(4) 24(2)

C(2) 5630(8) 1296(7) 3832(3) 20(2)

C(3) 4328(9) 879(7) 3742(4) 30(2)

C(4) 3826(11) -209(8) 3826(4) 44(3)

C(5) 4613(12) -855(8) 3977(4) 47(3)

C(6) 5921(13) -450(9) 4064(4) 54(3)

C(7) 6446(10) 640(8) 3992(4) 36(3)

C(8) 6469(9) 2487(7) 2787(3) 22(2)

C(9) 7183(11) 3385(8) 2465(4) 43(3)

C(10) 5041(10) 2180(9) 2612(4) 44(3)

C(11) 7093(12) 1524(8) 2741(4) 49(3)

C(12) 6251(9) 3286(8) 4625(3) 26(2)

C(13) 4851(10) 2720(9) 4759(4) 48(3)

C(14) 7218(10) 2783(8) 4908(4) 39(3)

C(15) 6455(10) 4474(7) 4759(4) 31(2)

C(16) 7585(10) 6750(8) 3014(4) 43(3)

C(17) 8192(11) 7005(8) 4123(4) 44(3)

C(18) 10317(10) 7108(8) 3367(5) 55(4)

C(19) 10809(9) 4684(9) 3087(4) 39(3)

C(20) 9461(9) 3008(7) 3775(4) 30(2)

Appendix

- 154 -

C(21) 10726(10) 5062(9) 4232(4) 41(3)

C(22) 4144(9) 8514(7) 1315(3) 22(2)

C(23) 4603(10) 9700(7) 1286(3) 30(2)

C(24) 5918(10) 10173(8) 1332(4) 36(3)

C(25) 6315(12) 11289(9) 1292(4) 46(3)

C(26) 5453(14) 11926(9) 1203(4) 50(3)

C(27) 4158(14) 11457(9) 1158(4) 52(3)

C(28) 3726(12) 10336(8) 1194(4) 41(3)

C(29) 3829(9) 8261(7) 2260(3) 24(2)

C(30) 3041(13) 9101(10) 2358(4) 65(4)

C(31) 3223(10) 7251(8) 2537(4) 41(3)

C(32) 5223(10) 8649(10) 2438(4) 59(4)

C(33) 4252(10) 7910(8) 398(3) 30(2)

C(34) 3489(13) 8669(11) 158(4) 67(4)

C(35) 3812(13) 6813(9) 170(4) 60(4)

C(36) 5705(11) 8321(11) 315(4) 63(4)

C(37) 3040(11) 4003(8) 1778(4) 49(3)

C(38) 2431(11) 4059(8) 669(4) 44(3)

C(39) 310(10) 3713(8) 1447(5) 48(3)

C(40) -433(9) 5964(9) 1795(4) 43(3)

C(41) 921(10) 7835(9) 1209(4) 48(3)

C(42) -186(11) 5795(10) 650(4) 57(4)

C(43) -180(17) 209(14) 3445(7) 59(3)

C(44) -1099(17) -417(14) 3132(7) 58(3)

C(45) -949(16) -322(14) 2634(7) 58(2)

C(46) 75(15) 387(13) 2440(7) 58(2)

C(47) 979(17) 1008(14) 2750(6) 60(2)

C(48) 829(17) 908(15) 3251(7) 60(3)

C(49) 210(20) 473(17) 1887(7) 58(3)

C(43A) 798(17) 917(14) 2044(7) 58(3)

C(44A) 1381(17) 1418(14) 2465(7) 59(3)

C(45A) 931(16) 1088(14) 2929(7) 59(3)

C(46A) -134(15) 231(13) 2969(7) 58(2)

C(47A) -748(17) -263(14) 2547(6) 58(2)

C(48A) -289(17) 75(14) 2084(7) 58(2)

C(49A) -640(20) -111(17) 3469(8) 60(3)

C(50) 120(20) -463(18) -179(10) 106(6)

C(51) -640(30) -620(20) 236(10) 106(6)

C(52) -730(20) 250(20) 530(10) 107(6)

C(53) -70(30) 1260(20) 404(11) 109(6)

C(54) 680(20) 1409(19) -10(11) 107(6)

C(55) 780(30) 558(19) -303(11) 106(6)

C(56) 250(30) -1390(20) -499(12) 120(7)

Appendix

- 155 -

C(57) 575(16) 499(14) 4873(6) 52(3)

C(58) 807(18) -512(14) 4941(8) 53(3)

C(59) -138(17) -1326(14) 5128(7) 55(3)

C(60) -1333(18) -1140(15) 5253(8) 57(3)

C(61) -1572(16) -130(15) 5187(7) 56(3)

C(62) -620(17) 686(15) 5000(8) 53(3)

C(63) 1600(20) 1369(17) 4669(9) 59(5)

Appendix

- 156 -









palladium





Chem Eur J 2011 17 4890-4895



Matthias Driess















Appendix

- 157 -

75 Curriculum Vitae

Personal Data



Nationality Chinese

Education




Bachelor Chemistry










appropriately cited

Wenyuan Wang

Berlin Juli 2012






























Table of contents

i

TABLE OF CONTENTS

1 INTRODUCTION 1





2 MOTIVATION 21


























Table of contents

ii






































Table of contents

iii

6 REFERENCES 129

7 APPENDIX 138






Introduction

- 1 -

1 INTRODUCTION






effect[1]













is maximal[4]










Introduction

- 2 -














silanone I3[9]









elements[11]



Introduction

- 3 -








The


Very




The bonding


0 donor-



bonds of ns2rarrp


orbitals[3 12d]





Introduction

- 4 -















and






Ge single[13f]






Introduction

- 5 -


reported by







order of three










species[12c]









(Scheme 16)



Introduction

- 6 -










II



The



[29]) was reported




II and Pb






this work

Introduction

- 7 -










SiIV







With these new





Introduction

- 8 -










The donor














Introduction

- 9 -







I23 with a Si0=Si




I





I











Introduction

- 10 -

I28[40]











reagents[43]


with a Ge0=Ge

0













Introduction

- 11 -






Jambor showed that








compound I32











Introduction

- 12 -




and I41[50]







minus) Nevertheless












synthetic chemists




Surprisingly X-ray



was









Introduction

- 13 -



















Introduction

- 14 -













II halides (ArE





Wright 1997


I52 Lappert 1997

SnNMe2

Sn

Me2N

NR

NR

NN

SiMe3

E

(Me3Si)2N

E

Me3Si

N(SiMe3)2

N

N

SiMe3

Sn

(Me3Si)2N

Sn

Me3Si

N(SiMe3)2

Lappert 1994


NN

N N

SnSn

SiMe3

SiMe3

Me3Si

Me3Si

I53 Lappert 1997

NN

N N

SnSn

SiMe3

SiMe3

Me3Si

Me3Si

Sn

Sn

Power 2005

I56 E = Ge R = Dip

I57 E = Sn R = Tip

R

RE

NH2

E

H2N

R

R








Introduction

- 15 -





and with





germylene I63[64]





(I65-I74) were






(aLSi-O-Si

aL

aL = PhC(

tBuN)2


Introduction

- 16 -


I77[68]


and









II Pb

II like I79

were presented[69]











Introduction

- 17 -






while







shown in detail















State of

Development


Introduction

- 18 -






and bis-stannylenes

















Introduction

- 19 -



prepared[74]






donor groups[72 76]
















Introduction

- 20 -


have received more






Motivation

- 21 -

2 MOTIVATION


























Motivation

- 22 -












- 23 -







and

(nacnac)GeCl3 2[82]




germanium derivates




derivative 3[83]




(nacnac)Ge-NH-



spectroscopy (1H


analyses



- 24 -












1H- and














but









- 25 -














35728(7) N1-C4 1382(3) C1-C2 1516(3) C2-C3 1411(3) C3-C4 1371(3)

C4-C5 1508(3) C2-Ge1-N1 843(1) C4-N1-Ge1 1130(1) C3-C2-C1 1202(2)

C3-C2-Ge1 1116(2) C1-C2-Ge1 1281(2) C4-C3-C2 1174(2) C3-C4-N1

1135(2) C3-C4-C5 1254(2)






- 26 -












1905(2) N1-C2 1329(3) N2-C4 1332(3) C1-C2 1518(3) C2-C3 1394(3)

C3-C4 1394(3) C4-C5 1512(3) N3-Ge1-N1 9720(8) N3-Ge1-N2 8876(9)


1227(2) C4-C3-C2 1269(3) N2-C4-C3 1239(3)


- 27 -























- 28 -








have been


species 5[83]











have been











- 29 -




and longer
















Ge2rsquo 1184(3) N2-C4-C3 1220(3)


cluster 5 The




- 30 -






cluster






- 31 -








compounds[93]







correlation[96]


The


approximation)[98]


potential



IGLO program[99]


theory[100]

The B3LYP[96a 101]


quality were









- 32 -































- 33 -














σ-character






150 pm abovea)


200 pm abovea)






a)



- 34 -


ring)
























- 35 -








(I27


I bonds










13C









- 36 -








ppm in the 119







The new GeI-Ge



I example Their







I


(257-








- 37 -

















Ge2 2549(1) Ge1-N1 2015(4) Ge1-N2 2038(4) Ge2-N3 1951(4) Ge2-C31

1903(5) N1-Ge1-N2 8867(15) N1-Ge1-Ge2 10430(11) N2-Ge1-Ge2


- 38 -

10149(12) C31-Ge2-N3 8447(19) C31-Ge2-Ge1 11890(15) N3-Ge2-Ge1


N3 1964(2) Ge1-C31 1915(3) N2-Sn1-N1 8288(8) N2-Sn1-Ge1 9542(5)


Ge1-Sn1 10200(6)


















- 39 -


I dimers






- 1206

LUMO

- 3911

HOMO

- 1138

LUMO

- 4024

HOMO

E [eV]

6a 8a

- 1206

LUMO

- 3911

HOMO

- 1138

LUMO

- 4024

HOMO

E [eV]

6a 8a















- 40 -







products[81-83 109]





benzenamine 9[111]




or (Z)-N-isopropyl








- 41 -

Et2O - 78degCnBuLi

Et2O - 78degCN

Dip

9

N

Dip

10

Li

N

Ph Dip

Cl

11

12

N

NH

Ph

Dip

Dip

Et2O - 78degC

N

Ph iPr

Cl

19

20

NH

N

Ph

Dip

iPr













respectively








- 42 -

N1C1

C2

C3 N2

Ph Dip

Dip

N1C1

C2

C3 N2

Ph iPr

Dip

1356

1386

1445

1309

1377

1360

1305

1452

12 20

HH





C13 14349(18) C1-C2 13769(19) C1-C4 15136(18) N2-C3 13046(16) N2-

C25 14297(17) C2-C3 14515(18) C2-C7 15257(18) N1-C1-C2 12221(12)

C1-C2-C3 12230(12) N2-C3-C2 12212(12) For 20 N1-C1 1309(2) N1-C17

1418(2) C1-C2 1445(2) C1-C4 1522(2) N2-C3 1356(2) N2-C14 1461(2)

C2-C3 1386(2) C2-C7 1524(2) C3-C8 1495(2) N1-C1-C2 12080(15) C1-

C2-C3 12151(15) N2-C3-C2 12288(15)






complex[27]



- 43 -























- 44 -



















published in 2006




22956(7) N1-C1 1342(3) N1-C14 1458(3) C1-C2 1397(3) C1-C8 1502(3)

N2-C3 1333(3) N2-C26 1463(2) C2-C3 1415(3) C2-C7 1522(3) C3-C4


- 45 -

1509(3) C4-C5 1522(3) N1-Ge1-N2 9123(7) N1-Ge1-Cl1 9560(5) N2-Ge1-

Cl1 9392(5) C1-N1-Ge1 12568(13) N1-C1-C2 12352(17) C1-C2-C3

12503(19) N2-C3-C2 12440(18) C3-N2-Ge1 12515(13)




N1-C8 1442(4) N2-C1 1408(4) N2-C20 1454(4) C1-C2 1359(4) C2-C3

1461(4) C1-C32 1498(4) C2-C7 1525(4) C3-C4 1360(4) N1-Ge1-N2

9509(11) C3-N1-Ge1 300(2) N1-C3-C2 1176(3) C1-C2-C3 1267(3) C2-C1-

N2 1241(3) C1-N2-Ge1 1259(2)











- 46 -











The 1H- and









154 ppm)[114]





and 3308 cmndash1


)[115]



- 47 -

= 3643 cmndash1




)[114]









due to the





[114]




N2 2017(2) Ge1-N3 1829(3) N1-C1 1349(4) C1-C2 1395(4) N2-C3

1336(4) C2-C3 1417(4) C3-C4 1509(4) N3-Ge1-N2 9503(11) N3-Ge1-N1

9709(13) N2-Ge1-N1 8932(10) C1-N1-Ge1 1253(2) C3-N2-Ge1 1247(2)

For 18 Ge1-O1 18249(18) Ge1-N2 20054(17) Ge1-N1 20071(16) N1-C1


- 48 -

1340(3) C1-C2 1402(3) N2-C3 1331(3) C2-C3 1419(3) C3-C4 1509(3)


12597(14) C3-N2-Ge1 12515(14)
















- 49 -









23 respectively














In compound 23 GeIV



center are





of the GeIV



- 50 -










Ge1-O1 18265(12) Ge1-N1 20908(15) O1-C6 1418(2) N1-C1 1284(2) N2-

C7 1272(2) C1-C6 1525(2) C6-C7 1539(2) Cl1-Ge1-O1 9789(4) Cl1-Ge1-

N1 9422(4) O1-Ge1-N1 8158(6) Ge1-N1-C1 11291(12) N1-C1-C6

11484(16) C1-C6-O1 10975(14) C6-O1-Ge1 11838(10) N2-C7-C6

11778(17) For 23 Ge1-Cl1 21339(7) Ge1-Cl2 21375(9) Ge1-N1 1798(2)

Ge1-N2 1788(2) N1-C1 1430(3) C1-C2 1339(4) C2-C3 1486(4) C3-C4

1326(4) N2-C3 1441(3) N2-Ge1-N1 10554(10) N2-Ge1-Cl1 11208(7) N1-


10276(3) C1-C2-C3 1266(2) C4-C3-N2 1209(2) C2-C4-C3 1208(3)





- 51 -







IIL [E = Si Ge Sn X











(aLSi-O-Si

aL

aL = PhC(


silylene I24[37]

(aLSi-Si




in








- 52 -





in 53 yield




in 76 yield The





tBu groups at δ =



Si-NMR spectrum of


- 53 -








aLSiO

iPr) (δ = -

135 ppm)[31b]

respectively


















package[101c 119]






The


- 54 -



(Figure 313)




20349(16) Cl2-Si2 22017(11) Si2-O1 1581(8) Si2-N3 1798(2) Si2-N4

1968(2) Si1-O1 1562(8) Si1-N2 1750(10) Si1-N1 1994(6) Si1-O1-Si2

1680(6)




1652(2) Si1-N1 1896(3) Si1-N2 1902(3) Si2-N3 1888(2) Si2-N4 1908(3)


N3 10196(11) O1-Si2-N4 10481(12) N1-Si1-N2 6815(10) N3-Si2-N4

6855(11)


- 55 -








29[32a]








- 56 -



















2216(2) pm][120]


(21395(8) pm)[121]









(2130-2146 pm)[121]





- 57 -

29

[Si][Si]

O

Ni

[Si] [Si]

Ni

CO CO

[Si] [Si]

Ni

N N tButBu

Si

N N DipDip

Si

[Si] = [Si] =

29a 29b

2207 2216

2191 2197689deg

934deg

1084deg 1019deg

1708 1701

2139 2139





Si1-N1 18929(19) Si1-N2 1875(2) Si2-O1 17081(17) Si2-N3 18776(19)


6941(9) N3-Si2-N4 6954(8)







- 58 -


Phosphasilene













oligomerize[126c]















- 59 -


aLSiCl



aL) 31






was easily


26[31a]





The 29





[31b] One





ppm)[31b]


- 60 -







aLSi-P




iPr2 derivative

[31b] The Si1-P1


pm) in the aLSi-P



subunit






- 61 -


10854(8)












72 yield





tBu






P-NMR spectrum



- 62 -








Phosphasilene[128]





(tBu3Si)2SiSi(Si














N2-Si1-N1 7078(11) P1-Si1-P1rsquo 10766(4)


- 63 -



















aLSiCl (1870(2) pm and 1917(2) pm)





- 64 -


















silylene 30 (0920)




- 65 -




























The


- 66 -




(Scheme 327)




















- 67 -





(Scheme 329) The



Si-N






(right)




N1 1832(7) Si1-N2 1827(7) Si1-N3 1705(7) Si2-N3 1780(7) Si3-N3



1248(4) Si2-N3-Si3 1179(4)


- 68 -















I58[61]

and

I64[65]










- 69 -












compound 35[33b]



13C-

and 29









- 70 -


singlet in the 29



tBu

iPr)

[31b]






31G(d)][101c 119]











(R = tBu

iPr)



- 71 -






by theoretical

calculation






O2-C3 13028


complex 36






36[33b]


(Scheme 333)


- 72 -













IV atom Si1 and the









complex[72b 77 135]




- 73 -


-Pd













23038(11) Si1-O1 1694(3) Si1-N1 1789(4) Si2-O2 1675(3) Si2-N5 1862(3)



Si2Si1

C1

Pd

Si3

213 pm

233 pm236 pm

230 pm

O1 O2


- 74 -

7861(11) Si2-Pd1-C1 7681(11) Si3-Pd1-C1 16783(12)


tBu groups









The 29



complexes[71 137]





The



)[135c 135f 136a]









335


- 75 -
















minus1


donor than PIII





minus1


- 76 -



and the first bis-






aLSi-Fc-Si


aLGe-Fc-Ge



PhD thesis[33a]









quantitatively














- 77 -






Si-NMR spectrum










The GeII centers






tBuC(N-Dip)2)




bidentate ligand


- 78 -




1979(9) Ge(2)-C(7) 1983(11) Ge(1)-N(1) 2027(8) Ge(1)-N(2) 2006(8)

Ge(2)-N(3) 2022(7) Ge(2)-N(4) 2037(7) C(1)-Ge(1)-N(2) 983(3) C(1)-Ge(1)-

N(1) 955(3) N(2)-Ge(1)-N(1) 653(3) C(7)-Ge(2)-N(3) 953(4) C(7)-Ge(2)-


Ge2-C8 19774(19) Ge1-N1 20261(16) Ge1-N2 20247(17) Ge2-N3

20402(15) Ge2-N4 20162(16) C1-Ge1-N1 9662(7) C1-Ge1-N2 9445(7) N1-


6459(6)




(Figure 323)


- 79 -







ferrocene molecules

6 9 0 6 9 5 7 0 0 7 0 5 7 1 0 7 1 5 7 2 0

m z

0

1 0

2 0

3 0

4 0

5 0

6 0

7 0

8 0

9 0

1 0 0

0

1 0

2 0

3 0

4 0

5 0

6 0

7 0

8 0

9 0

1 0 0

Re

lative

Abu

nda

nce

7 0 3 3 2 9

7 0 4 3 3 2

7 0 5 3 3 47 0 1 3 3 4

7 0 6 3 2 96 9 0 2 4 9 6 9 5 2 2 5 7 1 7 3 4 57 1 0 4 7 3

7 0 3 3 3 1

7 0 4 3 3 4

7 0 5 3 3 87 0 1 3 3 6

7 0 6 3 3 17 1 0 3 3 5

N L 3 1 3 E 7


N L 4 9 7 E 5


p a C hrg 1





- 80 -


recently[139]






transition-metals




0[32a


complex I65-Mo[66b]



[140] was





I

complex 41[33a]


42[33a]




- 81 -











42 δ = 699 737 and 891 ppm) In the 29













complex 41a[141]



[142] (21348(5) pm)


[143] (2228(2) pm) in


[141] (22060(6) and 22017(6) pm)






- 82 -





21252(14) Co1-Si2 21200(14) Si1-C6 1894(5) Si2-C11 1887(5) Si1-N1


9389(5) N1-Si1-N2 6847(15) N3-Si2-N4 6866(16) C6-Si1-Co1 13254(14)



- 83 -

C11 1961(4) Ge1-N1 2020(3) Ge1-N2 2031(3) Ge2-N3 2041(3) Ge2-N4

2029(3) Ge1-Co1-Ge2 9279(2) N1-Ge1-N2 6490(11) N3-Ge2-N4 6485(11)

C6-Ge1-Co1 13280(10) C11-Ge2-Co1 13140(10)



(2262(1) pm) and


4-((


and 25036(3) pm)[90d]


















- 84 -


tBu groups at δ =





of 41 In the 13






(ν = 1968 cmminus1

)[141]










tBu groups at δ =



Si-



- 85 -



C-



tBuO)SirarrFe(CO)4





)[71]
















2)-C(sp

3) coupling




- 86 -




expected[148]




Thus the catalytic


(Scheme 342)








- 87 -














- 88 -














Summary

- 89 -









in 33 yield








with KC8


in very low yield


dianion (CBD2-


core

Summary

- 90 -



and





in










Summary

- 91 -








was obtained by








in high yield










activation

Summary

- 92 -














[32a]



Summary

- 93 -







silylene 30[128]




product 31[128]










Summary

- 94 -









by 13-dilithium



as orange




SiIV




Summary

- 95 -











furnished





CoI complex 41


I complex 42

[33a]


Summary

- 96 -



are not shown












2)-C(sp

3)

cross-coupling[147]



Summary

- 97 -


probed[148-150]






- 98 -


51 General section




















dichloromethane





- 99 -









1H 400 MHz

13C


Si-NMR spectra were



The 1H and

13C








119Sn

1H external SnMe4








)












- 100 -






peak)























- 101 -










tBu [152]



9 (C5H10)C=N-Dip [111] 39 aLGeCl [41]



- 102 -











(030 g 083 mmol 33)





1H NMR (40013 MHz THF-D8 298K) δ = 108 (d

3JHH = 7 Hz 6 H




13C





378 Found C 5764 H 694 N 367




- 103 -

mmol 31)

NHN

GeN

Dip

DipDip

C41H59GeN3 MW 66657



1H NMR (40013 MHz C6D6 298K) δ = 091 (d

3JHH = 68 Hz 6 H


3JHH =





13C




C NCMe)

EI-MS mz () 6674 (03 [M]+) 4912 (100 [M -

iPr2C6H3NH]

+)


C 7354 H 868 N 613














- 104 -






C66H100Ge4K2N4O2 MW 135028


Found C 7821 H 999 N 281


C46H65Ge2N3 MW 80531








017 mmol 66)




- 105 -

1H NMR (40013 MHz C6D6 298K) δ = 107 (d

3JHH = 7 Hz 12 H


3JHH = 7




3JHH = 7 Hz 2 H



arom H)

13C






NCMe)





C 6884 H 800 N 516










- 106 -



dark red crystals



1H NMR (40013 MHz C6D6 298K) δ = 085 (d

3JHH = 7 Hz 6 H


3JHH = 7


3JHH = 7 Hz 6 H CHMe2) 129 (d




3JHH



721 (m 9 H arom H)

13C






NCMe)

119Sn NMR

(C6D6) δ = -197

UV-vis λ [nm] = 314 (15000) 363 (14500) 541 (2800)




Found C 6444 H 764 N 477


- 107 -


C37H48N2 MW 52079














1H NMR (40013 MHz CDCl3 298K) δ = 117 (d

3JHH = 7 Hz 6 H


3JHH = 7




arom H)

13C





CN) 1658 (Ph-CN)



8518 H 927 N 547


- 108 -


N

N

Ph

Dip

Dip

Cl

Ge












1H NMR (40013 MHz C6D6 298K) δ = 097 (d

3JHH = 7 Hz 3 H


3JHH = 7

Hz 3 H CHMe2) 121-127 (m 9 H CHMe2) 128-139 (m




3JHH = 7 Hz 1 H



13C





295 (Cy-CH2) 315 (Cy-CH2) 1089 (Cy-CCN) 1234-1476

(arom C) 1651 (Cy-CN) 1688 (Ph-CN)



Found C 7073 H 762 N 457


- 109 -


C37H46GeN2 MW 59142


ylidene 15[113]









1H NMR (40013 MHz C6D6 298K) δ = 115 (d

3JHH = 7 Hz 6 H


3JHH = 7




3JHH =

44 Hz 1 H C=CH) 675- 725 (m 11 H arom H)

13C




1117 (Cy-CCN) 1236-1431 (arom C) 1473 1474 (Cy-CN

Ph-CN)

IR (KBr cm-1

) 704 (s) 787 (s) 939 (m) 1104 (s) 1135 (s) 1204 (s) 1248 (s)

1296 (s) 1322 (s) 1365 (s) 1439 (s) 1461 (s) 1535 (m) 1600

(s) 2822 (m) 2865 (s) 2922 (s) 2957 (w) 3022 (w) 3061 (m)



C 7495 H 800 N 484


- 110 -


C37H49GeN3 MW 60845








1H NMR (40013 MHz C6D6 298K) δ = 106 (d

3JHH = 7 Hz 3 H



154 (s 2 H NH2) 200-213 (m 4 H Cy-CH2) 346 (sept


3JHH = 7 Hz 1 H



13C





293 (Cy-CH2) 315 (Cy-CH2) 1023 (Cy-CCN) 1234-1462

(arom C) 1643 (Cy-CN) 1669 (Ph-CN)

IR (KBr cm-1

) 561 (s) 704 (s) 752 (s) 796 (s) 839 (m) 922 (s) 1096 (s)

1143 (s) 1174 (s) 1252 (s) 1304 (s) 1360 (s) 1430 (s) 1543

(s) 2865 (m) 2961 (s) 3021 (w) 3048 (m) 3343 (w) 3430

(w)


C 7272 H 810 N 683


- 111 -










1H NMR (40013 MHz C6D6 298K) δ = 111 (d

3JHH = 7 Hz 3 H



166 (s 1 H OH) 195-221 (m 4 H Cy-CH2) 335 (sept


3JHH = 7 Hz 1 H



13C





291 (Cy-CH2) 314 (Cy-CH2) 1028 (Cy-CCN) 1233-1464

(arom C) 1647 (Cy-CN) 1666 (Ph-CN)

IR(KBr cm-1

) 561 (s) 713 (s) 743 (s) 770 (s) 791 (s) 839 (s) 926 (m)

1056 (m) 1104 (s) 1148 (s) 1170 (s) 1257 (s) 1313 (s) 1339

(s) 1365 (s) 1430 (s) 1470 (s) 1539 (s) 2861 (s) 2961 (s)

3018 (w) 3057 (m) 3643 (m)




- 112 -

Found C 7300 H 786 N 464


C28H38N2 MW 40230













1H NMR (40013 MHz CDCl3 298K) δ = 109 (d

3JHH = 7 Hz 6 H


3JHH = 7




1203 (d 3JHH = 7 Hz 1 H NH)

13C




(Cy-CCN) 1226 1228 1275 1282 1284 1371 1389

1453 (arom C) 1576 (Cy-CN) 1673 (PhCN)



- 113 -


8270 H 977 N 679













1H NMR (40013 MHz C6D6 298K) δ = 106 (d

3JHH = 7 Hz 3 H


3JHH = 7






3JHH = 7 Hz


1 H arom H) 705-724 (m 7 H arom H)

13C





- 114 -

293 (Cy-CH2) 312 (Cy-CH2) 537 (CHMe2) 1068 (Cy-

CCN) 1239 1250 1267 1271 1288 1294 1388 1410

1446 1469 (arom C) 1620 (Cy-CN) 1654 (Ph-CN)


Found C 6426 H 725 N 551










287 mmol 57 )



1H NMR (40013 MHz C6D6 298K) δ = 113 (d

3JHH = 7 Hz 6 H


3JHH = 7




3JHH =

42 Hz 1 H C=CH) 701-726 (m 8 H arom H)

13C


CH2) 247 (CHMe2) 254 (Cy-CH2) 257 (CHMe2) 286


- 115 -


1125 (Cy-CCN) 1248 1287 1296 1354 1391 1411

1421 1490 (arom C) 1682 (Cy-CN) 1709 (Ph-CN)


Found C 6203 H 517 N 679




tBu













(s 2 H SiHCl) 733- 746 (m 10 H arom H)

13C


1276 1285 1297 1337 (arom C) 1711 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = -1110

IR(KBr cm-1

) 606 (s) 658 (m) 711 (s) 733 (s) 760 (s) 789 (s) 934 (s)

1068 (s) 1200 (s) 1269 (s) 1378 (s) 1486 (s) 1550 (s) 1566

(s) 1612 (s) 1783 (w) 1826 (w) 1950 (w) 1969 (w) 2000


- 116 -

(w) 2135 (s) 2188 (s) 2909 (s) 2934 (s) 2971 (s) 3232 (m)



Found C 5971 H 797 N 913


C30H46N4OSi2 MW 53488










731(m 10 H arom H)

13C


1277 1291 1299 1349 (arom C) 1623 (NCN)

29Si

1H NMR (7949 MHz C6D6 298K) δ = -161

IR(KBr cm-1

) 608 (s) 709 (s) 746 (s) 790 (s) 892 (m) 972 (s) 1032 (m)

1070 (m) 1208 (s) 1268 (m) 1359 (s) 1412 (s) 1446 (s)

1476 (s) 1577 (m) 1648 (m) 1778 (w) 1826 (w) 1899 (w)

1970 (w) 2248 (w) 2867 (s) 2902 (s) 2928 (s) 2964 (s)

3065 (m)


- 117 -



Found C 6688 H 857 N 1046












(m 4 H CH2) 295 (m 4 H CH2) 504 (s 4 H =CH) 686-

707 (m 10 H arom H)

13C


(CMe3) 760 (=CH) 1277 1293 1296 1335 (arom C)

1690 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = 328

IR(KBr cm-1

) 607 (s) 644 (s) 698 (s) 750 (s) 792 (s) 925 (m) 1021 (m)

1075 (s) 1209 (s) 1267 (s) 1320 (m) 1361 (s) 1407 (s)

1444 (s) 1475 (s) 1578 (m) 1647 (m) 1775 (w) 1823 (w)


- 118 -

1902 (w) 1962 (w) 2280 (w) 2791 (s) 2855 (s) 2913 (s)

2975 (s) 3023 (m) 3063 (w)



Found C 6387 H 837 N 805


C21H41N2PSi3 MW 43679


(302 mg 102





085 mmol 83)



1H NMR (40013 MHz C6D6 298K) δ = 058 (d

3JP-H = 44 Hz 18 H


734-741 (m 3 H arom H)

13C

1H NMR (10061 MHz C6D6 298K) δ = 44 (d

3JC-P = 100 Hz


1292 1293 1344 (arom C) 1572 (d 3JC-P = 95 Hz

NCN)

29Si

1H NMR (7949 MHz C6D6 298K) δ = 31 (d

1JSi-P = 229 Hz


31P NMR (81012 MHz C6D6 298K) δ = - 2110


- 119 -



C30H46N4P2Si2 MW 58083





mg 025 mmol 72)




733 (m 10 H arom H)

13C


(CMe3) 1256 1276 1294 1359 (arom C) 1710 (NCN)

29Si

1H NMR (7949 MHz THF-D8 298K) δ = 267 (t

1JSi-P = 998 Hz)

31P NMR (81012 MHz THF-D8 298K) δ = - 1649


5802361


- 120 -




(336 mg 114










689 Found C 4195 H 701 N 706


C44H66N4O2Si2 MW 73919









- 121 -





174 (s 18 H ArC(CH3)3) 693 - 713 (m 8 H arom H) 754


13C


(NC(CH3)3) 350 (ArC(CH3)3) 530 (NC(CH3)3) 1096

1243 1276 1295 1297 1313 1341 1552 (arom C)

1636 (NCN)

29Si

1H NMR (7949 MHz C6D6 298K) δ = -240


Found C 7075 H 930 N 756


C88H132N8O4PdSi4 MW 158480








- 122 -






(s 9 H C(CH3)3) 114 (s 9 H C(CH3)3) 116 (s 9 H

C(CH3)3) 131 (s 9 H C(CH3)3) 139 (s 9 H C(CH3)3)155

(s 9 H C(CH3)3) 168 (s 9 H C(CH3)3) 177 (s 9 H

C(CH3)3) 180 (s 9 H C(CH3)3) 185 (s 9 H C(CH3)3) 212

(s 9 H C(CH3)3) 659 (s 1 H SiH) 686- 789 (m 22 H


13C

1H NMR (10061 MHz C6D6 298K) δ = 309 (C(CH3)3) 311

(C(CH3)3) 314 (C(CH3)3) 316 (C(CH3)3) 318 (C(CH3)3)

319 (C(CH3)3) 320 (C(CH3)3) 322 (C(CH3)3) 328

(C(CH3)3) 332 (C(CH3)3) 333 (C(CH3)3) 343 (C(CH3)3)

349 350 351 357 526 527 537 539 540 541 542

561 1112 1225 1236 1243 1256 1258 1271 1285

1287 1289 1291 1293 1294 1302 1303 1318 1323

1324 1326 1340 1342 1378 1380 1381 1409 1430

1533 1559 1585 1613 1622 1654 1731 1742

29Si


658 (LSiPd)

IR(KBr cm-1

) 623 (m) 706 (m) 764 (m) 860 (m) 1056 (m) 1108 (m) 1206

(m) 1272 (m) 1365 (m) 1418 (s) 1446 (m) 1476 (m) 1446

(m) 1476 (m) 1495 (m) 1591 (m) 2135 (w) 2875(m) 2906

(s) 2964 (s) 3061 (w)


707 Found C 6616 H 875 N 676


- 123 -















451 (t 3JHH = 15 Hz 4 H FeCH) 472 (t

3JHH = 15 Hz 4 H

FeCH) 692- 707 (m 10 H arom H)

13C



1294 1305 1349 (arom C) 1604 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = 433



Found C 6803 H 767 N 778


- 124 -















(t 3JHH = 16 Hz 4 H FeCH) 471 (t

3JHH = 16 Hz 4 H


H)

13C



1290 1302 1369 (arom C) 1659 (NCN)


C 6655 H 701 N 707


- 125 -


tBu

N

N

tBu

PhSi

tBu

N

N

tBu

Ph Si

Co

Fe













440 (t 3JHH = 16 Hz 4 H FeCH) 461 (t

3JHH = 16 Hz 4 H


692- 696 (m 6 H arom H) 720- 723 (m 2 H arom H)

13C



(SiC) 1291 1297 1300 1343 (arom C) 1673 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = 820



Found C 6612 H 724 N 686


- 126 -


tBu

N

N

tBu

PhGe

tBu

N

N

tBu

Ph Ge

Co

Fe













438 (t 3JHH = 15 Hz 4 H FeCH) 459 (t

3JHH = 15 Hz 4 H


695- 698 (m 6 H arom H) 714- 718 (m 2 H arom H)

13C



(GeC) 1287 1296 1300 1361(arom C) 1680 (NCN)


Found C 5942 H 664 N 590


- 127 -











461 (m 4 H FeCH) 476 (m 4 H FeCH) 523 (s 10 H

CoCH) 683- 695 (m 6 H arom H) 702- 706 (m 2 H

arom H) 745- 748 (m 2 H arom H)

13C



(CoCH) 1287 1296 1300 1324 (arom C) 1687 (NCN)

2078 (br CO)

29Si

1H NMR (7949 MHz C6D6 298K) δ = 857

IR(KBr cm-1

) 500 (m) 539 (w) 564 (m) 628 (s) 703 (m) 757 (s) 792 (m)

825 (w) 1028 (m) 1081 (w) 1146 (m) 1199 (s) 1275 (m)

1360 (m) 1388 (m) 1417 (s) 1438 (w) 1474 (m) 1520 (s)

1641 (s) 1888 (s) 2869 (s) 2901 (m) 2926 (m) 2965 (s)

1520 (s) 3097 (w)



- 128 -

556 Found C 6287 H 630 N 571


C48H54Fe3N4O8Si2 MW 103867










H) 736- 739 (m 2 H arom H)

13C



1287 1303 1308 (arom C) 1704 (NCN) 2169 (CO)

29Si

1H NMR (7949 MHz C6D6 298K) δ = 1050

IR(KBr cm-1

) 630 (s) 765 (w) 1028 (m) 1035 (m) 1200 (m) 1370 (w)

1400 (m) 1474 (w) 1609 (w) 1648 (w) 1900 (s) 1948 (s)

1996(w) 2026 (s) 2865 (w) 2930 (m) 2965 (m)


539 Found C 5623 H 517 N 566

References

- 129 -

6 REFERENCES



353


3877












2010 16 436


1955 77 884











Chem Int Ed 2003 42 2222




Chem Soc 1994 116 3667







References

- 130 -










5683













11366


Science 2008 321 1069




12315











9701




References

- 131 -

2008 47 1650






121 347







Int Ed 2011 50 5374


1991 1302


2004 630 2090



4130


1994 33 1156


Int Ed 1997 36 261


Inorg Chem 1997 36 5202



2008 130 12268



127 17530











References

- 132 -


















2012 51 399


5058















2011 44 588









References

- 133 -










20 1190



Allg Chem 2001 627 836




Soc 1996 118 10457





3655






Soc 2011 133 5103



Soc 1996 118 6317


Chem Rev 2005 105 3842










Phys 2000 2 2137

References

- 134 -



Phys Rev 1988 37 785









Chem Soc 2006 128 1023










2005 127 3516


2004 43 1419



2343




2003 pp 2217













References

- 135 -



CT 2004
























2868

















References

- 136 -












Chem Int Ed 2007 46 4141



2009 82 793







Chem 2011 50 8502




1804

















7162

References

- 137 -




Appendix

- 138 -

7 APPENDIX

71 Abbreviations



mmol millimole(ar)





















Et ethyl t triplet







IR infrared

K Kelvin


functions aL PhC(

tBuN)2








Appendix

- 139 -

GeN

N

GeN

Dip

Dip

DipCl

N

SnN

Dip

Dip

GeNN

SnN

Dip

DipDip

N

Dip

6 7


1 2 3 4

5 8 9

10 11 12 13 14

15 16 17 18

19 20 21 22

Appendix

- 140 -

23 24 25 26

27 28 29

30 31 32 33

34 35 36

tBu

N

N

tBu

Ph

Si

Cl

37 38 39 40

Appendix

- 141 -

tBu

N

N

tBu

PhSi

tBu

N

N

tBu

Ph Si

Co

Fe

41 42 43

44 45 46

47a 47b 48a 48b

Appendix

- 142 -



Compound 3 4 5

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C50 H88 Ge2 K2 N2 O4

100460

150(2)

71073

Triclinic

P-1

106989(7) pm

114137(7) pm

122625(8) pm

74158(6) deg

76395(6) deg

83400(5) deg

139807(16)

1

1193

1263

536

028 x 02 x 018

326 to 2500deg

-12lt=hlt=12

-13lt=klt=13

-14lt=llt=14

12268

4910 [R(int) = 00358]

996


100000 and 094847


4910 0 281

0940

R1 = 00328 wR2 = 00638

R1 = 00538 wR2 = 00666

0456 and -0223

C41 H5 Ge N3

66650

150(2)

71073

Triclinic

P-1

91129(6) pm

113531(7) pm

190282(10) pm

100360(5) deg

101854(5) deg

98627(5) deg

185918(19)

2

1191

0855

716

039 x 012 x 007

297 to 2500deg

-10lt=hlt=10

-13lt=klt=13

-22lt=llt=22

14570

6543 [R(int) = 00560]

998


0943 and 0777


6543 0 420

0785

R1 = 00399 wR2 = 00513

R1 = 00853 wR2 = 00566

0577 and -0317

C66 H102 Ge4 K2 N4 O2

135208

150(2)

71073

Monoclinic

P21n

12370(3) pm

148433(14) pm

188725(19) pm

90059(8)deg

96311(14)deg

90082(13)deg

34442(10)

2

1304

1892

1416

030 x 025 x 015

292 to 2500deg

-14lt=hlt=14

-15lt=klt=17

-14lt=llt=22

17371

6032 [R(int) = 00487]

995

Analytical

0807 and 0584


6032 2 364

0911

R1 = 00424 wR2 = 00801

R1 = 00874 wR2 = 00885

0497 and -0457

Appendix

- 143 -


Compound 6 8 12

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C46 H65 Ge2 N3

80519

150(2)

71073

Monoclinic

C2c

44536(2) pm

98204(5) pm

218135(10) pm

90deg

116030(4)deg

90deg

85727(7)

8

1248

1436

3408

038 x 024 x 010

305 to 2500deg

-49lt=hlt=52

-10lt=klt=11

-24lt=llt=25

20162

7493 [R(int) = 00954]

992


100000 and 074676


7493 0 476

0917

R1 = 00559 wR2 = 00778

R1 = 01461 wR2 = 00966

0590 and -0578

C46 H65 Ge N3 Sn

85129

150(2)

71073

Triclinic

P-1

867780(10) pm

120514(4) pm

210797(6) pm

96333(2)deg

97393(2)deg

99141(2)deg

213908(10)

2

1322

1320

888

016 x 014 x 012

295 to 2500deg

-10lt=hlt=10

-14lt=klt=14

-25lt=llt=25

16936

7496 [R(int) = 00251]

994


100000 and 099037


7496 0 495

1001

R1 = 00309 wR2 = 00706

R1 = 00437 wR2 = 00733

1468 and -0424

C37 H48 N2

52077

150(2)

71073

Triclinic

P-1

108485(5) pm

127284(7) pm

132348(4) pm

65748(4)deg

86290(3)deg

71699(5)deg

157759(12)

2

1096

0063

568

029 x 022 x 018

298 to 2500deg

-11lt=hlt=12

-15lt=klt=15

-15lt=llt=15

13428

5541 [R(int) = 00203]

998

None

09888 and 09820


5541 0 364

1029

R1 = 00439 wR2 = 00900

R1 = 00633 wR2 = 00963

0188 and -0193

Appendix

- 144 -


Compound 14 16 17

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C37 H46 Cl Ge N2

62680

150(2)

71073

Monoclinic

P21c

117621(2) pm

175495(4) pm

166051(3) pm

90deg

107053(2)deg

90deg

327691(11)

4

1270

1044

1324

040 x 032 x 022

342 to 2500deg

-13lt=hlt=13

-19lt=klt=20

-19lt=llt=18

16923

5742 [R(int) = 00250]

997


100000 and 082078


5742 0 378

1044

R1 = 00328 wR2 = 00709

R1 = 00496 wR2 = 00742

0736 and -0362

C37 H46 Ge N2

59135

150(2)

71073

Triclinic

P-1

108388(6) pm

127885(7) pm

132778(4) pm

66971(4)deg

85749(3)deg

71833(5)deg

160695(13)

2

1222

0980

628

029 x 015 x 007

307 to 2500deg

-12lt=hlt=12

-15lt=klt=15

-15lt=llt=15

13501

5636 [R(int) = 00366]

996


100000 and 092510


5636 0 369

1031

R1 = 00489 wR2 = 01180

R1 = 00691 wR2 = 01242

0539 and -0501

C37 H49 Ge N3

60838

150(2)

71073

Monoclinic

P21c

117714(4) pm

174309(6) pm

166868(6) pm

90deg

106866(4)deg

90deg

32766(2)

4

1233

0964

1296

030 x 023 x 019

342 to 2500deg

-8lt=hlt=13

-10lt=klt=20

-19lt=llt=16

12816

5749 [R(int) = 00325]

998


100000 and 095425


5749 0 378

1060

R1 = 00464 wR2 = 01084

R1 = 00699 wR2 = 01133

1717 and -0738

Appendix

- 145 -


Compound 18 20 22

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C37 H48 Ge N2 O

60936

150(2)

71073

Monoclinic

P21c

117560(3) pm

174116(5) pm

166421(4) pm

90deg

106992(3)deg

90deg

325778(15)

4

1242

0971

1296

031 x 014 x 005

343 to 2500deg

-13lt=hlt=13

-20lt=klt=20

-19lt=llt=19

23624

5720 [R(int) = 00371]

998


100000 and 083390


5720 0 379

1018

R1 = 00336 wR2 = 00752

R1 = 00516 wR2 = 00789

0521 and -0366

C28 H38 N2

40260

150(2)

71073

Monoclinic

P21c

94924(4) pm

256583(9) pm

107465(5) pm

90deg

110403(5)deg

90deg

245320(18)

4

1090

0063

880

017 x 015 x 013

343 to 2500deg

-11lt=hlt=10

-30lt=klt=27

-12lt=llt=11

8561

4313 [R(int) = 00209]

997


100000 and 099057


4313 0 281

1041

R1 = 00476 wR2 = 01015

R1 = 00771 wR2 = 01083

0253 and -0194

C28 H37 Cl Ge N2 O

52564

150(2)

71073

Triclinic

P-1

89021(3) pm

107319(4) pm

151176(6) pm

75734(4)deg

74781(3)deg

75311(3)deg

132282(8)

2

1320

1281

552

020 x 012 x 008

354 to 2500deg

-10lt=hlt=10

-12lt=klt=12

-15lt=llt=17

9246

4654 [R(int) = 00211]

997


100000 and 086160


4654 0 304

0946

R1 = 00274 wR2 = 00579

R1 = 00386 wR2 = 00597

0394 and -0264

Appendix

- 146 -


Compound 23 27 28

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C28 H36 Cl2 Ge N2

54408

150(2)

71073

Monoclinic

C2c

279616(13) pm

113538(3) pm

177729(7) pm

90deg

109718(5)deg

90deg

53115(4)

8

1361

1374

2272

021 x 017 x 015

332 to 2500deg

-25lt=hlt=33

-7lt=klt=13

-21lt=llt=20

10951

4663 [R(int) = 00459]

997


100000 and 091223


4663 0 304

0856

R1 = 00372 wR2 = 00584

R1 = 00684 wR2 = 00620

0589 and -0533


60780

150(2)

71073

Monoclinic

P21c

121593(5) pm

162045(6) pm

171248(7) pm

90deg

98177(4)deg

90deg

33399(2)

4

1209

0295

1304

030 x 015 x 005

335 to 2500deg

-14lt=hlt=13

-16lt=klt=19

-20lt=llt=20

23741

5865 [R(int) = 00491]

998


100000 and 086688


5865 172 490

1035

R1 = 00543 wR2 = 01080

R1 = 00905 wR2 = 01194

0310 and -0412

C30 H46 N4 O Si2

53489

150(2)

71073

Orthorhombic

Fdd2

31188(2) pm

39120(3) pm

102620(6) pm

90deg

90deg

90deg

125204(14)

16

1135

0141

4640

031 x 011 x 007

334 to 2500deg

-28lt=hlt=36

-46lt=klt=45

-12lt=llt=12

11517

4372 [R(int) = 00656]

997


100000 and 097469


4372 1 346

0897

R1 = 00488 wR2 = 00604

R1 = 00754 wR2 = 00650

0328 and -0229

Appendix

- 147 -


Compound 29 30 31

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C38 H58 N4 Ni O Si2

70177

150(2)

71073

Triclinic

P-1

98776(8) pm

129530(11) pm

155488(13) pm

81634(7)deg

83316(7)deg

82826(7)deg

19430(3)

2

1200

0594

756

020 x 009 x 007

330 to 2500deg

-11lt=hlt=11

-15lt=klt=13

-18lt=llt=18

14961

6828 [R(int) = 00414]

997


100000 and 091998


6828 0 474

0948

R1 = 00386 wR2 = 00807

R1 = 00605 wR2 = 00853

0407 and -0240

C21 H41 N2 P Si3

43680

173(2)

71073

Orthorhombic

Pbca

193556(7) pm

142399(4) pm

199777(6) pm

90deg

90deg

90deg

55063(3)

8

1054

0239

1904

039 x 036 x 016

351 to 2500deg

-13lt=hlt=23

-16lt=klt=16

-23lt=llt=22

19912

4836 [R(int) = 00961]

998


09627 and 09125


4836 18 287

0906

R1 = 00571 wR2 = 00889

R1 = 01270 wR2 = 01032

0316 and -0214

C44 H60 N4 P2 Si2

76308

173(2)

71073

Monoclinic

C2c

23841(3) pm

101993(12) pm

19369(2) pm

90deg

108346(12)deg

90deg

44703(9)

4

1134

0184

1640

076 x 057 x 055

353 to 2500deg

-28lt=hlt=28

-12lt=klt=12

-20lt=llt=23

16197

3927 [R(int) = 00447]

997


09053 and 08725


3927 0 251

1034

R1 = 00618 wR2 = 01393

R1 = 00843 wR2 = 01489

0721 and -0649

Appendix

- 148 -



Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)


140312

150(2)

71073

Triclinic

P-1

105159(4) pm

127622(6) pm

269391(12) pm

90310(4)deg

90855(3)deg

102927(3)deg

35232(3)

2

1323

1000

1456

013 x 012 x 009

336 to 2500deg

-12lt=hlt=12

-15lt=klt=15

-29lt=llt=32

25757

12396 [R(int) = 00546]

997


09154 and 08810


12396 536 816

2077

R1 = 01231 wR2 = 01906

R1 = 01495 wR2 = 01944

1510 and -4753

C91 H139 N8 O4 Pd Si4

162786

150(2)

71073

Triclinic

P-1

145970(8) pm

151441(15) pm

232982(16) pm

71358(8)deg

74666(5)deg

85365(6)deg

47063(6)

2

1149

0298

1750

019 x 013 x 011

327 to 2500deg

-17lt=hlt=17

-17lt=klt=18

-27lt=llt=27

41022

16531 [R(int) = 00735]

998


09679 and 09455


16531 284 1112

0908

R1 = 00558 wR2 = 01021

R1 = 01075 wR2 = 01128

0688 and -0448

C40 H54 Fe Ge2 N4

79190

150(2)

71073

Monoclinic

P21n

10532(3) pm

20258(5) pm

18990(5) pm

90deg

10542(3)deg

90deg

39060(19)

4

1347

1927

1648

012 x 008 x 005

322 to 2500deg

-6lt=hlt=12

-22lt=klt=24

-22lt=llt=21

16887

6870 [R(int) = 01353]

997


100000 and 073478


6870 213 498

1044

R1 = 00912 wR2 = 01786

R1 = 01680 wR2 = 02282

0570 and -1404

Appendix

- 149 -



Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C40 H54 Fe Ge2 N4

79190

150(2)

71073

Monoclinic

P21n

165582(11) pm

127695(7) pm

198175(12) pm

90deg

107428(7)deg

90deg

39979(4)

4

1316

1883

1648

012 x 011 x 009

337 to 2499deg

-16lt=hlt=19

-15lt=klt=15

-23lt=llt=23

29049

7015 [R(int) = 00329]

998


100000 and 052405


7015 0 436

1065

R1 = 00263 wR2 = 00574

R1 = 00318 wR2 = 00595

0357 and -0360


82692

150(2)

71073

Monoclinic

P21c

119176(7) pm

160794(9) pm

220424(13) pm

90deg

94402(5)deg

90deg

42115(4)

4

1304

0831

1752

015 x 013 x 007

323 to 2500deg

-14lt=hlt=14

-19lt=klt=17

-16lt=llt=26

17786

7404 [R(int) = 01111]

998


100000 and 075122


7404 0 490

1052

R1 = 00717 wR2 = 01045

R1 = 01208 wR2 = 01181

0467 and -0370


91592

150(2)

71073

Monoclinic

P21c

121662(3) pm

160596(3) pm

220073(5) pm

90deg

93549(2)deg

90deg

429163(16)

4

1418

2134

1896

015 x 011 x 008

336 to 2500deg

-14lt=hlt=14

-19lt=klt=19

-26lt=llt=26

33743

7539 [R(int) = 00521]

998


100000 and 068509


7539 0 521

1259

R1 = 00400 wR2 = 00965

R1 = 00536 wR2 = 01000

0376 and -0373

Appendix

- 150 -


following tables



2times10

3)


x y z U(eq)

N(1) 1159(1) 1176(1) 6836(1) 20(1)

C(1) 1706(2) 1650(1) 6995(1) 21(1)

N(2) -1293(2) 1547(1) 7057(1) 23(1)

C(2) 789(2) 2089(1) 7078(1) 20(1)

C(3) -626(2) 2021(1) 7158(1) 20(1)

C(4) 3331(2) 1741(1) 7112(2) 29(1)

C(5) 3920(2) 2283(1) 7590(2) 34(1)

C(6) 2795(2) 2681(1) 6772(2) 35(1)

C(7) 1375(2) 2643(1) 7102(2) 27(1)

C(8) -1522(2) 2482(1) 7295(2) 21(1)

C(9) -2759(2) 2643(1) 6227(2) 27(1)

C(10) -3571(2) 3077(1) 6331(2) 33(1)

C(11) -3169(2) 3358(1) 7498(2) 35(1)

C(12) -1948(2) 3199(1) 8573(2) 32(1)

C(13) -1133(2) 2765(1) 8467(2) 27(1)

C(14) -2537(2) 1417(1) 7503(2) 35(1)

C(15) -3250(3) 920(1) 6823(2) 61(1)

C(16) -1974(3) 1344(1) 9002(2) 65(1)

C(17) 2080(2) 741(1) 6834(2) 20(1)

C(18) 2353(2) 597(1) 5670(2) 23(1)

C(19) 3237(2) 160(1) 5724(2) 29(1)

C(20) 3821(2) -131(1) 6867(2) 32(1)

C(21) 3480(2) -1(1) 7977(2) 29(1)

C(22) 2598(2) 427(1) 7984(2) 23(1)

C(23) 2150(2) 562(1) 9174(2) 28(1)

C(24) 2101(2) 91(1) 10028(2) 39(1)

C(25) 3156(2) 987(1) 10029(2) 42(1)

C(26) 1602(2) 885(1) 4374(2) 29(1)

C(27) 2645(3) 974(1) 3586(2) 53(1)

C(28) 195(3) 588(1) 3539(2) 54(1)

Appendix

- 151 -


2times10

3)


x y z U(eq)

Ge(1) 4751(1) 5279(1) 3913(1) 24(1)

Cl(1) 4863(1) 7474(1) 3443(1) 35(1)

O(1) 2591(1) 5468(1) 4187(1) 20(1)

N(1) 4469(2) 5098(1) 2623(1) 17(1)

C(1) 3006(2) 5278(2) 2582(1) 16(1)

N(2) 1482(2) 7765(2) 2375(1) 20(1)

C(2) 2432(2) 5062(2) 1801(1) 21(1)

C(3) 1144(2) 4228(2) 2174(2) 31(1)

C(4) -158(2) 4793(2) 2933(2) 30(1)

C(5) 534(2) 4844(2) 3741(1) 21(1)

C(6) 1810(2) 5684(2) 3440(1) 17(1)

C(7) 1063(2) 7152(2) 3205(1) 18(1)

C(8) 820(2) 9172(2) 2096(1) 26(1)

C(9) 397(3) 9344(2) 1159(2) 40(1)

C(10) 2058(3) 9950(2) 2035(2) 43(1)

C(11) -95(2) 7719(2) 3998(1) 18(1)

C(12) 434(2) 8108(2) 4652(1) 22(1)

C(13) -648(2) 8637(2) 5376(1) 27(1)

C(14) -2259(2) 8769(2) 5459(2) 30(1)

C(15) -2795(2) 8370(2) 4815(2) 30(1)

C(16) -1724(2) 7845(2) 4085(1) 24(1)

C(17) 5786(2) 4690(2) 1889(1) 19(1)

C(18) 6546(2) 3361(2) 1997(1) 22(1)

C(19) 7868(2) 3005(2) 1310(2) 28(1)

C(20) 8423(2) 3902(2) 552(2) 29(1)

C(21) 7656(2) 5209(2) 464(1) 26(1)

C(22) 6329(2) 5635(2) 1128(1) 21(1)

C(23) 5549(2) 7085(2) 991(2) 26(1)

C(24) 6701(3) 7932(2) 989(2) 41(1)

C(25) 4931(3) 7520(2) 84(2) 40(1)

C(26) 6001(2) 2315(2) 2820(2) 27(1)

C(27) 5775(3) 1139(2) 2495(2) 40(1)

C(28) 7175(3) 1863(2) 3471(2) 38(1)

Appendix

- 152 -


2times10

3)


x y z U(eq)

Ge(1) 967(1) 7605(1) 1823(1) 18(1)

Cl(1) 1020(1) 9314(1) 2345(1) 29(1)

N(1) 1401(1) 6550(2) 2449(1) 19(1)

C(1) 1534(1) 5601(2) 2029(2) 16(1)

Cl(2) 198(1) 7116(1) 1640(1) 31(1)

N(2) 1101(1) 7630(2) 909(1) 15(1)

C(2) 1548(1) 5691(2) 1285(2) 15(1)

C(3) 1442(1) 6764(2) 777(2) 14(1)

C(4) 1615(1) 6867(2) 172(2) 19(1)

C(5) 1945(1) 5989(2) -42(2) 26(1)

C(6) 2098(1) 4966(2) 547(2) 22(1)

C(7) 1669(1) 4652(2) 844(2) 21(1)

C(8) 1625(1) 4444(2) 2470(2) 17(1)

C(9) 1229(1) 3875(2) 2611(2) 23(1)

C(10) 1291(1) 2785(2) 2983(2) 29(1)

C(11) 1764(2) 2263(3) 3232(2) 32(1)

C(12) 2169(1) 2832(3) 3121(2) 30(1)

C(13) 2101(1) 3920(2) 2737(2) 22(1)

C(14) 1621(1) 6630(2) 3327(2) 20(1)

C(15) 1219(1) 6848(3) 3699(2) 32(1)

C(16) 2052(1) 7524(2) 3583(2) 34(1)

C(17) 833(1) 8395(2) 248(2) 17(1)

C(18) 1019(1) 9542(2) 207(2) 19(1)

C(19) 745(1) 10248(3) -431(2) 29(1)

C(20) 315(1) 9844(3) -1011(2) 36(1)

C(21) 147(1) 8718(3) -973(2) 33(1)

C(22) 399(1) 7960(2) -350(2) 20(1)

C(23) 215(1) 6700(2) -377(2) 23(1)

C(24) 329(1) 6020(3) -1045(2) 34(1)

C(25) -341(1) 6612(3) -475(2) 31(1)

C(26) 1517(1) 10001(2) 789(2) 22(1)

C(27) 1914(1) 10083(3) 375(2) 32(1)

C(28) 1463(1) 11198(2) 1144(2) 36(1)

Appendix

- 153 -


2times10

3)


x y z U(eq)

Sn(1) 4689(1) 4918(1) 3222(1) 24(1)

Sn(2) 5822(1) 5994(1) 1674(1) 30(1)

Cl(1) 4488(3) 6215(2) 3883(1) 38(1)

Cl(2) 3266(2) 3378(2) 3638(1) 39(1)

Cl(3) 7188(2) 7769(2) 1449(1) 43(1)

Cl(4) 6104(3) 5090(3) 888(1) 57(1)

Si(1) 6825(2) 4259(2) 3587(1) 17(1)

Si(2) 8610(3) 6420(2) 3531(1) 28(1)

Si(3) 9814(2) 4466(2) 3664(1) 26(1)

Si(4) 3648(2) 6680(2) 1375(1) 21(1)

Si(5) 1981(3) 4463(2) 1299(1) 30(1)

Si(6) 649(3) 6348(2) 1247(1) 30(1)

N(1) 6586(7) 2924(5) 3299(3) 20(2)

N(2) 6484(6) 3264(5) 4080(3) 16(2)

N(3) 8389(7) 5001(5) 3582(3) 23(2)

N(4) 3751(7) 7937(6) 1722(3) 22(2)

N(5) 3959(8) 7800(6) 936(3) 27(2)

N(6) 2102(7) 5865(6) 1329(3) 24(2)

C(1) 6258(8) 2470(7) 3742(4) 24(2)

C(2) 5630(8) 1296(7) 3832(3) 20(2)

C(3) 4328(9) 879(7) 3742(4) 30(2)

C(4) 3826(11) -209(8) 3826(4) 44(3)

C(5) 4613(12) -855(8) 3977(4) 47(3)

C(6) 5921(13) -450(9) 4064(4) 54(3)

C(7) 6446(10) 640(8) 3992(4) 36(3)

C(8) 6469(9) 2487(7) 2787(3) 22(2)

C(9) 7183(11) 3385(8) 2465(4) 43(3)

C(10) 5041(10) 2180(9) 2612(4) 44(3)

C(11) 7093(12) 1524(8) 2741(4) 49(3)

C(12) 6251(9) 3286(8) 4625(3) 26(2)

C(13) 4851(10) 2720(9) 4759(4) 48(3)

C(14) 7218(10) 2783(8) 4908(4) 39(3)

C(15) 6455(10) 4474(7) 4759(4) 31(2)

C(16) 7585(10) 6750(8) 3014(4) 43(3)

C(17) 8192(11) 7005(8) 4123(4) 44(3)

C(18) 10317(10) 7108(8) 3367(5) 55(4)

C(19) 10809(9) 4684(9) 3087(4) 39(3)

C(20) 9461(9) 3008(7) 3775(4) 30(2)

Appendix

- 154 -

C(21) 10726(10) 5062(9) 4232(4) 41(3)

C(22) 4144(9) 8514(7) 1315(3) 22(2)

C(23) 4603(10) 9700(7) 1286(3) 30(2)

C(24) 5918(10) 10173(8) 1332(4) 36(3)

C(25) 6315(12) 11289(9) 1292(4) 46(3)

C(26) 5453(14) 11926(9) 1203(4) 50(3)

C(27) 4158(14) 11457(9) 1158(4) 52(3)

C(28) 3726(12) 10336(8) 1194(4) 41(3)

C(29) 3829(9) 8261(7) 2260(3) 24(2)

C(30) 3041(13) 9101(10) 2358(4) 65(4)

C(31) 3223(10) 7251(8) 2537(4) 41(3)

C(32) 5223(10) 8649(10) 2438(4) 59(4)

C(33) 4252(10) 7910(8) 398(3) 30(2)

C(34) 3489(13) 8669(11) 158(4) 67(4)

C(35) 3812(13) 6813(9) 170(4) 60(4)

C(36) 5705(11) 8321(11) 315(4) 63(4)

C(37) 3040(11) 4003(8) 1778(4) 49(3)

C(38) 2431(11) 4059(8) 669(4) 44(3)

C(39) 310(10) 3713(8) 1447(5) 48(3)

C(40) -433(9) 5964(9) 1795(4) 43(3)

C(41) 921(10) 7835(9) 1209(4) 48(3)

C(42) -186(11) 5795(10) 650(4) 57(4)

C(43) -180(17) 209(14) 3445(7) 59(3)

C(44) -1099(17) -417(14) 3132(7) 58(3)

C(45) -949(16) -322(14) 2634(7) 58(2)

C(46) 75(15) 387(13) 2440(7) 58(2)

C(47) 979(17) 1008(14) 2750(6) 60(2)

C(48) 829(17) 908(15) 3251(7) 60(3)

C(49) 210(20) 473(17) 1887(7) 58(3)

C(43A) 798(17) 917(14) 2044(7) 58(3)

C(44A) 1381(17) 1418(14) 2465(7) 59(3)

C(45A) 931(16) 1088(14) 2929(7) 59(3)

C(46A) -134(15) 231(13) 2969(7) 58(2)

C(47A) -748(17) -263(14) 2547(6) 58(2)

C(48A) -289(17) 75(14) 2084(7) 58(2)

C(49A) -640(20) -111(17) 3469(8) 60(3)

C(50) 120(20) -463(18) -179(10) 106(6)

C(51) -640(30) -620(20) 236(10) 106(6)

C(52) -730(20) 250(20) 530(10) 107(6)

C(53) -70(30) 1260(20) 404(11) 109(6)

C(54) 680(20) 1409(19) -10(11) 107(6)

C(55) 780(30) 558(19) -303(11) 106(6)

C(56) 250(30) -1390(20) -499(12) 120(7)

Appendix

- 155 -

C(57) 575(16) 499(14) 4873(6) 52(3)

C(58) 807(18) -512(14) 4941(8) 53(3)

C(59) -138(17) -1326(14) 5128(7) 55(3)

C(60) -1333(18) -1140(15) 5253(8) 57(3)

C(61) -1572(16) -130(15) 5187(7) 56(3)

C(62) -620(17) 686(15) 5000(8) 53(3)

C(63) 1600(20) 1369(17) 4669(9) 59(5)

Appendix

- 156 -









palladium





Chem Eur J 2011 17 4890-4895



Matthias Driess















Appendix

- 157 -

75 Curriculum Vitae

Personal Data



Nationality Chinese

Education




Bachelor Chemistry










appropriately cited

Wenyuan Wang

Berlin Juli 2012

Table of contents

ii






































Table of contents

iii

6 REFERENCES 129

7 APPENDIX 138






Introduction

- 1 -

1 INTRODUCTION






effect[1]













is maximal[4]










Introduction

- 2 -














silanone I3[9]









elements[11]



Introduction

- 3 -








The


Very




The bonding


0 donor-



bonds of ns2rarrp


orbitals[3 12d]





Introduction

- 4 -















and






Ge single[13f]






Introduction

- 5 -


reported by







order of three










species[12c]









(Scheme 16)



Introduction

- 6 -










II



The



[29]) was reported




II and Pb






this work

Introduction

- 7 -










SiIV







With these new





Introduction

- 8 -










The donor














Introduction

- 9 -







I23 with a Si0=Si




I





I











Introduction

- 10 -

I28[40]











reagents[43]


with a Ge0=Ge

0













Introduction

- 11 -






Jambor showed that








compound I32











Introduction

- 12 -




and I41[50]







minus) Nevertheless












synthetic chemists




Surprisingly X-ray



was









Introduction

- 13 -



















Introduction

- 14 -













II halides (ArE





Wright 1997


I52 Lappert 1997

SnNMe2

Sn

Me2N

NR

NR

NN

SiMe3

E

(Me3Si)2N

E

Me3Si

N(SiMe3)2

N

N

SiMe3

Sn

(Me3Si)2N

Sn

Me3Si

N(SiMe3)2

Lappert 1994


NN

N N

SnSn

SiMe3

SiMe3

Me3Si

Me3Si

I53 Lappert 1997

NN

N N

SnSn

SiMe3

SiMe3

Me3Si

Me3Si

Sn

Sn

Power 2005

I56 E = Ge R = Dip

I57 E = Sn R = Tip

R

RE

NH2

E

H2N

R

R








Introduction

- 15 -





and with





germylene I63[64]





(I65-I74) were






(aLSi-O-Si

aL

aL = PhC(

tBuN)2


Introduction

- 16 -


I77[68]


and









II Pb

II like I79

were presented[69]











Introduction

- 17 -






while







shown in detail















State of

Development


Introduction

- 18 -






and bis-stannylenes

















Introduction

- 19 -



prepared[74]






donor groups[72 76]
















Introduction

- 20 -


have received more






Motivation

- 21 -

2 MOTIVATION


























Motivation

- 22 -












- 23 -







and

(nacnac)GeCl3 2[82]




germanium derivates




derivative 3[83]




(nacnac)Ge-NH-



spectroscopy (1H


analyses



- 24 -












1H- and














but









- 25 -














35728(7) N1-C4 1382(3) C1-C2 1516(3) C2-C3 1411(3) C3-C4 1371(3)

C4-C5 1508(3) C2-Ge1-N1 843(1) C4-N1-Ge1 1130(1) C3-C2-C1 1202(2)

C3-C2-Ge1 1116(2) C1-C2-Ge1 1281(2) C4-C3-C2 1174(2) C3-C4-N1

1135(2) C3-C4-C5 1254(2)






- 26 -












1905(2) N1-C2 1329(3) N2-C4 1332(3) C1-C2 1518(3) C2-C3 1394(3)

C3-C4 1394(3) C4-C5 1512(3) N3-Ge1-N1 9720(8) N3-Ge1-N2 8876(9)


1227(2) C4-C3-C2 1269(3) N2-C4-C3 1239(3)


- 27 -























- 28 -








have been


species 5[83]











have been











- 29 -




and longer
















Ge2rsquo 1184(3) N2-C4-C3 1220(3)


cluster 5 The




- 30 -






cluster






- 31 -








compounds[93]







correlation[96]


The


approximation)[98]


potential



IGLO program[99]


theory[100]

The B3LYP[96a 101]


quality were









- 32 -































- 33 -














σ-character






150 pm abovea)


200 pm abovea)






a)



- 34 -


ring)
























- 35 -








(I27


I bonds










13C









- 36 -








ppm in the 119







The new GeI-Ge



I example Their







I


(257-








- 37 -

















Ge2 2549(1) Ge1-N1 2015(4) Ge1-N2 2038(4) Ge2-N3 1951(4) Ge2-C31

1903(5) N1-Ge1-N2 8867(15) N1-Ge1-Ge2 10430(11) N2-Ge1-Ge2


- 38 -

10149(12) C31-Ge2-N3 8447(19) C31-Ge2-Ge1 11890(15) N3-Ge2-Ge1


N3 1964(2) Ge1-C31 1915(3) N2-Sn1-N1 8288(8) N2-Sn1-Ge1 9542(5)


Ge1-Sn1 10200(6)


















- 39 -


I dimers






- 1206

LUMO

- 3911

HOMO

- 1138

LUMO

- 4024

HOMO

E [eV]

6a 8a

- 1206

LUMO

- 3911

HOMO

- 1138

LUMO

- 4024

HOMO

E [eV]

6a 8a















- 40 -







products[81-83 109]





benzenamine 9[111]




or (Z)-N-isopropyl








- 41 -

Et2O - 78degCnBuLi

Et2O - 78degCN

Dip

9

N

Dip

10

Li

N

Ph Dip

Cl

11

12

N

NH

Ph

Dip

Dip

Et2O - 78degC

N

Ph iPr

Cl

19

20

NH

N

Ph

Dip

iPr













respectively








- 42 -

N1C1

C2

C3 N2

Ph Dip

Dip

N1C1

C2

C3 N2

Ph iPr

Dip

1356

1386

1445

1309

1377

1360

1305

1452

12 20

HH





C13 14349(18) C1-C2 13769(19) C1-C4 15136(18) N2-C3 13046(16) N2-

C25 14297(17) C2-C3 14515(18) C2-C7 15257(18) N1-C1-C2 12221(12)

C1-C2-C3 12230(12) N2-C3-C2 12212(12) For 20 N1-C1 1309(2) N1-C17

1418(2) C1-C2 1445(2) C1-C4 1522(2) N2-C3 1356(2) N2-C14 1461(2)

C2-C3 1386(2) C2-C7 1524(2) C3-C8 1495(2) N1-C1-C2 12080(15) C1-

C2-C3 12151(15) N2-C3-C2 12288(15)






complex[27]



- 43 -























- 44 -



















published in 2006




22956(7) N1-C1 1342(3) N1-C14 1458(3) C1-C2 1397(3) C1-C8 1502(3)

N2-C3 1333(3) N2-C26 1463(2) C2-C3 1415(3) C2-C7 1522(3) C3-C4


- 45 -

1509(3) C4-C5 1522(3) N1-Ge1-N2 9123(7) N1-Ge1-Cl1 9560(5) N2-Ge1-

Cl1 9392(5) C1-N1-Ge1 12568(13) N1-C1-C2 12352(17) C1-C2-C3

12503(19) N2-C3-C2 12440(18) C3-N2-Ge1 12515(13)




N1-C8 1442(4) N2-C1 1408(4) N2-C20 1454(4) C1-C2 1359(4) C2-C3

1461(4) C1-C32 1498(4) C2-C7 1525(4) C3-C4 1360(4) N1-Ge1-N2

9509(11) C3-N1-Ge1 300(2) N1-C3-C2 1176(3) C1-C2-C3 1267(3) C2-C1-

N2 1241(3) C1-N2-Ge1 1259(2)











- 46 -











The 1H- and









154 ppm)[114]





and 3308 cmndash1


)[115]



- 47 -

= 3643 cmndash1




)[114]









due to the





[114]




N2 2017(2) Ge1-N3 1829(3) N1-C1 1349(4) C1-C2 1395(4) N2-C3

1336(4) C2-C3 1417(4) C3-C4 1509(4) N3-Ge1-N2 9503(11) N3-Ge1-N1

9709(13) N2-Ge1-N1 8932(10) C1-N1-Ge1 1253(2) C3-N2-Ge1 1247(2)

For 18 Ge1-O1 18249(18) Ge1-N2 20054(17) Ge1-N1 20071(16) N1-C1


- 48 -

1340(3) C1-C2 1402(3) N2-C3 1331(3) C2-C3 1419(3) C3-C4 1509(3)


12597(14) C3-N2-Ge1 12515(14)
















- 49 -









23 respectively














In compound 23 GeIV



center are





of the GeIV



- 50 -










Ge1-O1 18265(12) Ge1-N1 20908(15) O1-C6 1418(2) N1-C1 1284(2) N2-

C7 1272(2) C1-C6 1525(2) C6-C7 1539(2) Cl1-Ge1-O1 9789(4) Cl1-Ge1-

N1 9422(4) O1-Ge1-N1 8158(6) Ge1-N1-C1 11291(12) N1-C1-C6

11484(16) C1-C6-O1 10975(14) C6-O1-Ge1 11838(10) N2-C7-C6

11778(17) For 23 Ge1-Cl1 21339(7) Ge1-Cl2 21375(9) Ge1-N1 1798(2)

Ge1-N2 1788(2) N1-C1 1430(3) C1-C2 1339(4) C2-C3 1486(4) C3-C4

1326(4) N2-C3 1441(3) N2-Ge1-N1 10554(10) N2-Ge1-Cl1 11208(7) N1-


10276(3) C1-C2-C3 1266(2) C4-C3-N2 1209(2) C2-C4-C3 1208(3)





- 51 -







IIL [E = Si Ge Sn X











(aLSi-O-Si

aL

aL = PhC(


silylene I24[37]

(aLSi-Si




in








- 52 -





in 53 yield




in 76 yield The





tBu groups at δ =



Si-NMR spectrum of


- 53 -








aLSiO

iPr) (δ = -

135 ppm)[31b]

respectively


















package[101c 119]






The


- 54 -



(Figure 313)




20349(16) Cl2-Si2 22017(11) Si2-O1 1581(8) Si2-N3 1798(2) Si2-N4

1968(2) Si1-O1 1562(8) Si1-N2 1750(10) Si1-N1 1994(6) Si1-O1-Si2

1680(6)




1652(2) Si1-N1 1896(3) Si1-N2 1902(3) Si2-N3 1888(2) Si2-N4 1908(3)


N3 10196(11) O1-Si2-N4 10481(12) N1-Si1-N2 6815(10) N3-Si2-N4

6855(11)


- 55 -








29[32a]








- 56 -



















2216(2) pm][120]


(21395(8) pm)[121]









(2130-2146 pm)[121]





- 57 -

29

[Si][Si]

O

Ni

[Si] [Si]

Ni

CO CO

[Si] [Si]

Ni

N N tButBu

Si

N N DipDip

Si

[Si] = [Si] =

29a 29b

2207 2216

2191 2197689deg

934deg

1084deg 1019deg

1708 1701

2139 2139





Si1-N1 18929(19) Si1-N2 1875(2) Si2-O1 17081(17) Si2-N3 18776(19)


6941(9) N3-Si2-N4 6954(8)







- 58 -


Phosphasilene













oligomerize[126c]















- 59 -


aLSiCl



aL) 31






was easily


26[31a]





The 29





[31b] One





ppm)[31b]


- 60 -







aLSi-P




iPr2 derivative

[31b] The Si1-P1


pm) in the aLSi-P



subunit






- 61 -


10854(8)












72 yield





tBu






P-NMR spectrum



- 62 -








Phosphasilene[128]





(tBu3Si)2SiSi(Si














N2-Si1-N1 7078(11) P1-Si1-P1rsquo 10766(4)


- 63 -



















aLSiCl (1870(2) pm and 1917(2) pm)





- 64 -


















silylene 30 (0920)




- 65 -




























The


- 66 -




(Scheme 327)




















- 67 -





(Scheme 329) The



Si-N






(right)




N1 1832(7) Si1-N2 1827(7) Si1-N3 1705(7) Si2-N3 1780(7) Si3-N3



1248(4) Si2-N3-Si3 1179(4)


- 68 -















I58[61]

and

I64[65]










- 69 -












compound 35[33b]



13C-

and 29









- 70 -


singlet in the 29



tBu

iPr)

[31b]






31G(d)][101c 119]











(R = tBu

iPr)



- 71 -






by theoretical

calculation






O2-C3 13028


complex 36






36[33b]


(Scheme 333)


- 72 -













IV atom Si1 and the









complex[72b 77 135]




- 73 -


-Pd













23038(11) Si1-O1 1694(3) Si1-N1 1789(4) Si2-O2 1675(3) Si2-N5 1862(3)



Si2Si1

C1

Pd

Si3

213 pm

233 pm236 pm

230 pm

O1 O2


- 74 -

7861(11) Si2-Pd1-C1 7681(11) Si3-Pd1-C1 16783(12)


tBu groups









The 29



complexes[71 137]





The



)[135c 135f 136a]









335


- 75 -
















minus1


donor than PIII





minus1


- 76 -



and the first bis-






aLSi-Fc-Si


aLGe-Fc-Ge



PhD thesis[33a]









quantitatively














- 77 -






Si-NMR spectrum










The GeII centers






tBuC(N-Dip)2)




bidentate ligand


- 78 -




1979(9) Ge(2)-C(7) 1983(11) Ge(1)-N(1) 2027(8) Ge(1)-N(2) 2006(8)

Ge(2)-N(3) 2022(7) Ge(2)-N(4) 2037(7) C(1)-Ge(1)-N(2) 983(3) C(1)-Ge(1)-

N(1) 955(3) N(2)-Ge(1)-N(1) 653(3) C(7)-Ge(2)-N(3) 953(4) C(7)-Ge(2)-


Ge2-C8 19774(19) Ge1-N1 20261(16) Ge1-N2 20247(17) Ge2-N3

20402(15) Ge2-N4 20162(16) C1-Ge1-N1 9662(7) C1-Ge1-N2 9445(7) N1-


6459(6)




(Figure 323)


- 79 -







ferrocene molecules

6 9 0 6 9 5 7 0 0 7 0 5 7 1 0 7 1 5 7 2 0

m z

0

1 0

2 0

3 0

4 0

5 0

6 0

7 0

8 0

9 0

1 0 0

0

1 0

2 0

3 0

4 0

5 0

6 0

7 0

8 0

9 0

1 0 0

Re

lative

Abu

nda

nce

7 0 3 3 2 9

7 0 4 3 3 2

7 0 5 3 3 47 0 1 3 3 4

7 0 6 3 2 96 9 0 2 4 9 6 9 5 2 2 5 7 1 7 3 4 57 1 0 4 7 3

7 0 3 3 3 1

7 0 4 3 3 4

7 0 5 3 3 87 0 1 3 3 6

7 0 6 3 3 17 1 0 3 3 5

N L 3 1 3 E 7


N L 4 9 7 E 5


p a C hrg 1





- 80 -


recently[139]






transition-metals




0[32a


complex I65-Mo[66b]



[140] was





I

complex 41[33a]


42[33a]




- 81 -











42 δ = 699 737 and 891 ppm) In the 29













complex 41a[141]



[142] (21348(5) pm)


[143] (2228(2) pm) in


[141] (22060(6) and 22017(6) pm)






- 82 -





21252(14) Co1-Si2 21200(14) Si1-C6 1894(5) Si2-C11 1887(5) Si1-N1


9389(5) N1-Si1-N2 6847(15) N3-Si2-N4 6866(16) C6-Si1-Co1 13254(14)



- 83 -

C11 1961(4) Ge1-N1 2020(3) Ge1-N2 2031(3) Ge2-N3 2041(3) Ge2-N4

2029(3) Ge1-Co1-Ge2 9279(2) N1-Ge1-N2 6490(11) N3-Ge2-N4 6485(11)

C6-Ge1-Co1 13280(10) C11-Ge2-Co1 13140(10)



(2262(1) pm) and


4-((


and 25036(3) pm)[90d]


















- 84 -


tBu groups at δ =





of 41 In the 13






(ν = 1968 cmminus1

)[141]










tBu groups at δ =



Si-



- 85 -



C-



tBuO)SirarrFe(CO)4





)[71]
















2)-C(sp

3) coupling




- 86 -




expected[148]




Thus the catalytic


(Scheme 342)








- 87 -














- 88 -














Summary

- 89 -









in 33 yield








with KC8


in very low yield


dianion (CBD2-


core

Summary

- 90 -



and





in










Summary

- 91 -








was obtained by








in high yield










activation

Summary

- 92 -














[32a]



Summary

- 93 -







silylene 30[128]




product 31[128]










Summary

- 94 -









by 13-dilithium



as orange




SiIV




Summary

- 95 -











furnished





CoI complex 41


I complex 42

[33a]


Summary

- 96 -



are not shown












2)-C(sp

3)

cross-coupling[147]



Summary

- 97 -


probed[148-150]






- 98 -


51 General section




















dichloromethane





- 99 -









1H 400 MHz

13C


Si-NMR spectra were



The 1H and

13C








119Sn

1H external SnMe4








)












- 100 -






peak)























- 101 -










tBu [152]



9 (C5H10)C=N-Dip [111] 39 aLGeCl [41]



- 102 -











(030 g 083 mmol 33)





1H NMR (40013 MHz THF-D8 298K) δ = 108 (d

3JHH = 7 Hz 6 H




13C





378 Found C 5764 H 694 N 367




- 103 -

mmol 31)

NHN

GeN

Dip

DipDip

C41H59GeN3 MW 66657



1H NMR (40013 MHz C6D6 298K) δ = 091 (d

3JHH = 68 Hz 6 H


3JHH =





13C




C NCMe)

EI-MS mz () 6674 (03 [M]+) 4912 (100 [M -

iPr2C6H3NH]

+)


C 7354 H 868 N 613














- 104 -






C66H100Ge4K2N4O2 MW 135028


Found C 7821 H 999 N 281


C46H65Ge2N3 MW 80531








017 mmol 66)




- 105 -

1H NMR (40013 MHz C6D6 298K) δ = 107 (d

3JHH = 7 Hz 12 H


3JHH = 7




3JHH = 7 Hz 2 H



arom H)

13C






NCMe)





C 6884 H 800 N 516










- 106 -



dark red crystals



1H NMR (40013 MHz C6D6 298K) δ = 085 (d

3JHH = 7 Hz 6 H


3JHH = 7


3JHH = 7 Hz 6 H CHMe2) 129 (d




3JHH



721 (m 9 H arom H)

13C






NCMe)

119Sn NMR

(C6D6) δ = -197

UV-vis λ [nm] = 314 (15000) 363 (14500) 541 (2800)




Found C 6444 H 764 N 477


- 107 -


C37H48N2 MW 52079














1H NMR (40013 MHz CDCl3 298K) δ = 117 (d

3JHH = 7 Hz 6 H


3JHH = 7




arom H)

13C





CN) 1658 (Ph-CN)



8518 H 927 N 547


- 108 -


N

N

Ph

Dip

Dip

Cl

Ge












1H NMR (40013 MHz C6D6 298K) δ = 097 (d

3JHH = 7 Hz 3 H


3JHH = 7

Hz 3 H CHMe2) 121-127 (m 9 H CHMe2) 128-139 (m




3JHH = 7 Hz 1 H



13C





295 (Cy-CH2) 315 (Cy-CH2) 1089 (Cy-CCN) 1234-1476

(arom C) 1651 (Cy-CN) 1688 (Ph-CN)



Found C 7073 H 762 N 457


- 109 -


C37H46GeN2 MW 59142


ylidene 15[113]









1H NMR (40013 MHz C6D6 298K) δ = 115 (d

3JHH = 7 Hz 6 H


3JHH = 7




3JHH =

44 Hz 1 H C=CH) 675- 725 (m 11 H arom H)

13C




1117 (Cy-CCN) 1236-1431 (arom C) 1473 1474 (Cy-CN

Ph-CN)

IR (KBr cm-1

) 704 (s) 787 (s) 939 (m) 1104 (s) 1135 (s) 1204 (s) 1248 (s)

1296 (s) 1322 (s) 1365 (s) 1439 (s) 1461 (s) 1535 (m) 1600

(s) 2822 (m) 2865 (s) 2922 (s) 2957 (w) 3022 (w) 3061 (m)



C 7495 H 800 N 484


- 110 -


C37H49GeN3 MW 60845








1H NMR (40013 MHz C6D6 298K) δ = 106 (d

3JHH = 7 Hz 3 H



154 (s 2 H NH2) 200-213 (m 4 H Cy-CH2) 346 (sept


3JHH = 7 Hz 1 H



13C





293 (Cy-CH2) 315 (Cy-CH2) 1023 (Cy-CCN) 1234-1462

(arom C) 1643 (Cy-CN) 1669 (Ph-CN)

IR (KBr cm-1

) 561 (s) 704 (s) 752 (s) 796 (s) 839 (m) 922 (s) 1096 (s)

1143 (s) 1174 (s) 1252 (s) 1304 (s) 1360 (s) 1430 (s) 1543

(s) 2865 (m) 2961 (s) 3021 (w) 3048 (m) 3343 (w) 3430

(w)


C 7272 H 810 N 683


- 111 -










1H NMR (40013 MHz C6D6 298K) δ = 111 (d

3JHH = 7 Hz 3 H



166 (s 1 H OH) 195-221 (m 4 H Cy-CH2) 335 (sept


3JHH = 7 Hz 1 H



13C





291 (Cy-CH2) 314 (Cy-CH2) 1028 (Cy-CCN) 1233-1464

(arom C) 1647 (Cy-CN) 1666 (Ph-CN)

IR(KBr cm-1

) 561 (s) 713 (s) 743 (s) 770 (s) 791 (s) 839 (s) 926 (m)

1056 (m) 1104 (s) 1148 (s) 1170 (s) 1257 (s) 1313 (s) 1339

(s) 1365 (s) 1430 (s) 1470 (s) 1539 (s) 2861 (s) 2961 (s)

3018 (w) 3057 (m) 3643 (m)




- 112 -

Found C 7300 H 786 N 464


C28H38N2 MW 40230













1H NMR (40013 MHz CDCl3 298K) δ = 109 (d

3JHH = 7 Hz 6 H


3JHH = 7




1203 (d 3JHH = 7 Hz 1 H NH)

13C




(Cy-CCN) 1226 1228 1275 1282 1284 1371 1389

1453 (arom C) 1576 (Cy-CN) 1673 (PhCN)



- 113 -


8270 H 977 N 679













1H NMR (40013 MHz C6D6 298K) δ = 106 (d

3JHH = 7 Hz 3 H


3JHH = 7






3JHH = 7 Hz


1 H arom H) 705-724 (m 7 H arom H)

13C





- 114 -

293 (Cy-CH2) 312 (Cy-CH2) 537 (CHMe2) 1068 (Cy-

CCN) 1239 1250 1267 1271 1288 1294 1388 1410

1446 1469 (arom C) 1620 (Cy-CN) 1654 (Ph-CN)


Found C 6426 H 725 N 551










287 mmol 57 )



1H NMR (40013 MHz C6D6 298K) δ = 113 (d

3JHH = 7 Hz 6 H


3JHH = 7




3JHH =

42 Hz 1 H C=CH) 701-726 (m 8 H arom H)

13C


CH2) 247 (CHMe2) 254 (Cy-CH2) 257 (CHMe2) 286


- 115 -


1125 (Cy-CCN) 1248 1287 1296 1354 1391 1411

1421 1490 (arom C) 1682 (Cy-CN) 1709 (Ph-CN)


Found C 6203 H 517 N 679




tBu













(s 2 H SiHCl) 733- 746 (m 10 H arom H)

13C


1276 1285 1297 1337 (arom C) 1711 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = -1110

IR(KBr cm-1

) 606 (s) 658 (m) 711 (s) 733 (s) 760 (s) 789 (s) 934 (s)

1068 (s) 1200 (s) 1269 (s) 1378 (s) 1486 (s) 1550 (s) 1566

(s) 1612 (s) 1783 (w) 1826 (w) 1950 (w) 1969 (w) 2000


- 116 -

(w) 2135 (s) 2188 (s) 2909 (s) 2934 (s) 2971 (s) 3232 (m)



Found C 5971 H 797 N 913


C30H46N4OSi2 MW 53488










731(m 10 H arom H)

13C


1277 1291 1299 1349 (arom C) 1623 (NCN)

29Si

1H NMR (7949 MHz C6D6 298K) δ = -161

IR(KBr cm-1

) 608 (s) 709 (s) 746 (s) 790 (s) 892 (m) 972 (s) 1032 (m)

1070 (m) 1208 (s) 1268 (m) 1359 (s) 1412 (s) 1446 (s)

1476 (s) 1577 (m) 1648 (m) 1778 (w) 1826 (w) 1899 (w)

1970 (w) 2248 (w) 2867 (s) 2902 (s) 2928 (s) 2964 (s)

3065 (m)


- 117 -



Found C 6688 H 857 N 1046












(m 4 H CH2) 295 (m 4 H CH2) 504 (s 4 H =CH) 686-

707 (m 10 H arom H)

13C


(CMe3) 760 (=CH) 1277 1293 1296 1335 (arom C)

1690 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = 328

IR(KBr cm-1

) 607 (s) 644 (s) 698 (s) 750 (s) 792 (s) 925 (m) 1021 (m)

1075 (s) 1209 (s) 1267 (s) 1320 (m) 1361 (s) 1407 (s)

1444 (s) 1475 (s) 1578 (m) 1647 (m) 1775 (w) 1823 (w)


- 118 -

1902 (w) 1962 (w) 2280 (w) 2791 (s) 2855 (s) 2913 (s)

2975 (s) 3023 (m) 3063 (w)



Found C 6387 H 837 N 805


C21H41N2PSi3 MW 43679


(302 mg 102





085 mmol 83)



1H NMR (40013 MHz C6D6 298K) δ = 058 (d

3JP-H = 44 Hz 18 H


734-741 (m 3 H arom H)

13C

1H NMR (10061 MHz C6D6 298K) δ = 44 (d

3JC-P = 100 Hz


1292 1293 1344 (arom C) 1572 (d 3JC-P = 95 Hz

NCN)

29Si

1H NMR (7949 MHz C6D6 298K) δ = 31 (d

1JSi-P = 229 Hz


31P NMR (81012 MHz C6D6 298K) δ = - 2110


- 119 -



C30H46N4P2Si2 MW 58083





mg 025 mmol 72)




733 (m 10 H arom H)

13C


(CMe3) 1256 1276 1294 1359 (arom C) 1710 (NCN)

29Si

1H NMR (7949 MHz THF-D8 298K) δ = 267 (t

1JSi-P = 998 Hz)

31P NMR (81012 MHz THF-D8 298K) δ = - 1649


5802361


- 120 -




(336 mg 114










689 Found C 4195 H 701 N 706


C44H66N4O2Si2 MW 73919









- 121 -





174 (s 18 H ArC(CH3)3) 693 - 713 (m 8 H arom H) 754


13C


(NC(CH3)3) 350 (ArC(CH3)3) 530 (NC(CH3)3) 1096

1243 1276 1295 1297 1313 1341 1552 (arom C)

1636 (NCN)

29Si

1H NMR (7949 MHz C6D6 298K) δ = -240


Found C 7075 H 930 N 756


C88H132N8O4PdSi4 MW 158480








- 122 -






(s 9 H C(CH3)3) 114 (s 9 H C(CH3)3) 116 (s 9 H

C(CH3)3) 131 (s 9 H C(CH3)3) 139 (s 9 H C(CH3)3)155

(s 9 H C(CH3)3) 168 (s 9 H C(CH3)3) 177 (s 9 H

C(CH3)3) 180 (s 9 H C(CH3)3) 185 (s 9 H C(CH3)3) 212

(s 9 H C(CH3)3) 659 (s 1 H SiH) 686- 789 (m 22 H


13C

1H NMR (10061 MHz C6D6 298K) δ = 309 (C(CH3)3) 311

(C(CH3)3) 314 (C(CH3)3) 316 (C(CH3)3) 318 (C(CH3)3)

319 (C(CH3)3) 320 (C(CH3)3) 322 (C(CH3)3) 328

(C(CH3)3) 332 (C(CH3)3) 333 (C(CH3)3) 343 (C(CH3)3)

349 350 351 357 526 527 537 539 540 541 542

561 1112 1225 1236 1243 1256 1258 1271 1285

1287 1289 1291 1293 1294 1302 1303 1318 1323

1324 1326 1340 1342 1378 1380 1381 1409 1430

1533 1559 1585 1613 1622 1654 1731 1742

29Si


658 (LSiPd)

IR(KBr cm-1

) 623 (m) 706 (m) 764 (m) 860 (m) 1056 (m) 1108 (m) 1206

(m) 1272 (m) 1365 (m) 1418 (s) 1446 (m) 1476 (m) 1446

(m) 1476 (m) 1495 (m) 1591 (m) 2135 (w) 2875(m) 2906

(s) 2964 (s) 3061 (w)


707 Found C 6616 H 875 N 676


- 123 -















451 (t 3JHH = 15 Hz 4 H FeCH) 472 (t

3JHH = 15 Hz 4 H

FeCH) 692- 707 (m 10 H arom H)

13C



1294 1305 1349 (arom C) 1604 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = 433



Found C 6803 H 767 N 778


- 124 -















(t 3JHH = 16 Hz 4 H FeCH) 471 (t

3JHH = 16 Hz 4 H


H)

13C



1290 1302 1369 (arom C) 1659 (NCN)


C 6655 H 701 N 707


- 125 -


tBu

N

N

tBu

PhSi

tBu

N

N

tBu

Ph Si

Co

Fe













440 (t 3JHH = 16 Hz 4 H FeCH) 461 (t

3JHH = 16 Hz 4 H


692- 696 (m 6 H arom H) 720- 723 (m 2 H arom H)

13C



(SiC) 1291 1297 1300 1343 (arom C) 1673 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = 820



Found C 6612 H 724 N 686


- 126 -


tBu

N

N

tBu

PhGe

tBu

N

N

tBu

Ph Ge

Co

Fe













438 (t 3JHH = 15 Hz 4 H FeCH) 459 (t

3JHH = 15 Hz 4 H


695- 698 (m 6 H arom H) 714- 718 (m 2 H arom H)

13C



(GeC) 1287 1296 1300 1361(arom C) 1680 (NCN)


Found C 5942 H 664 N 590


- 127 -











461 (m 4 H FeCH) 476 (m 4 H FeCH) 523 (s 10 H

CoCH) 683- 695 (m 6 H arom H) 702- 706 (m 2 H

arom H) 745- 748 (m 2 H arom H)

13C



(CoCH) 1287 1296 1300 1324 (arom C) 1687 (NCN)

2078 (br CO)

29Si

1H NMR (7949 MHz C6D6 298K) δ = 857

IR(KBr cm-1

) 500 (m) 539 (w) 564 (m) 628 (s) 703 (m) 757 (s) 792 (m)

825 (w) 1028 (m) 1081 (w) 1146 (m) 1199 (s) 1275 (m)

1360 (m) 1388 (m) 1417 (s) 1438 (w) 1474 (m) 1520 (s)

1641 (s) 1888 (s) 2869 (s) 2901 (m) 2926 (m) 2965 (s)

1520 (s) 3097 (w)



- 128 -

556 Found C 6287 H 630 N 571


C48H54Fe3N4O8Si2 MW 103867










H) 736- 739 (m 2 H arom H)

13C



1287 1303 1308 (arom C) 1704 (NCN) 2169 (CO)

29Si

1H NMR (7949 MHz C6D6 298K) δ = 1050

IR(KBr cm-1

) 630 (s) 765 (w) 1028 (m) 1035 (m) 1200 (m) 1370 (w)

1400 (m) 1474 (w) 1609 (w) 1648 (w) 1900 (s) 1948 (s)

1996(w) 2026 (s) 2865 (w) 2930 (m) 2965 (m)


539 Found C 5623 H 517 N 566

References

- 129 -

6 REFERENCES



353


3877












2010 16 436


1955 77 884











Chem Int Ed 2003 42 2222




Chem Soc 1994 116 3667







References

- 130 -










5683













11366


Science 2008 321 1069




12315











9701




References

- 131 -

2008 47 1650






121 347







Int Ed 2011 50 5374


1991 1302


2004 630 2090



4130


1994 33 1156


Int Ed 1997 36 261


Inorg Chem 1997 36 5202



2008 130 12268



127 17530











References

- 132 -


















2012 51 399


5058















2011 44 588









References

- 133 -










20 1190



Allg Chem 2001 627 836




Soc 1996 118 10457





3655






Soc 2011 133 5103



Soc 1996 118 6317


Chem Rev 2005 105 3842










Phys 2000 2 2137

References

- 134 -



Phys Rev 1988 37 785









Chem Soc 2006 128 1023










2005 127 3516


2004 43 1419



2343




2003 pp 2217













References

- 135 -



CT 2004
























2868

















References

- 136 -












Chem Int Ed 2007 46 4141



2009 82 793







Chem 2011 50 8502




1804

















7162

References

- 137 -




Appendix

- 138 -

7 APPENDIX

71 Abbreviations



mmol millimole(ar)





















Et ethyl t triplet







IR infrared

K Kelvin


functions aL PhC(

tBuN)2








Appendix

- 139 -

GeN

N

GeN

Dip

Dip

DipCl

N

SnN

Dip

Dip

GeNN

SnN

Dip

DipDip

N

Dip

6 7


1 2 3 4

5 8 9

10 11 12 13 14

15 16 17 18

19 20 21 22

Appendix

- 140 -

23 24 25 26

27 28 29

30 31 32 33

34 35 36

tBu

N

N

tBu

Ph

Si

Cl

37 38 39 40

Appendix

- 141 -

tBu

N

N

tBu

PhSi

tBu

N

N

tBu

Ph Si

Co

Fe

41 42 43

44 45 46

47a 47b 48a 48b

Appendix

- 142 -



Compound 3 4 5

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C50 H88 Ge2 K2 N2 O4

100460

150(2)

71073

Triclinic

P-1

106989(7) pm

114137(7) pm

122625(8) pm

74158(6) deg

76395(6) deg

83400(5) deg

139807(16)

1

1193

1263

536

028 x 02 x 018

326 to 2500deg

-12lt=hlt=12

-13lt=klt=13

-14lt=llt=14

12268

4910 [R(int) = 00358]

996


100000 and 094847


4910 0 281

0940

R1 = 00328 wR2 = 00638

R1 = 00538 wR2 = 00666

0456 and -0223

C41 H5 Ge N3

66650

150(2)

71073

Triclinic

P-1

91129(6) pm

113531(7) pm

190282(10) pm

100360(5) deg

101854(5) deg

98627(5) deg

185918(19)

2

1191

0855

716

039 x 012 x 007

297 to 2500deg

-10lt=hlt=10

-13lt=klt=13

-22lt=llt=22

14570

6543 [R(int) = 00560]

998


0943 and 0777


6543 0 420

0785

R1 = 00399 wR2 = 00513

R1 = 00853 wR2 = 00566

0577 and -0317

C66 H102 Ge4 K2 N4 O2

135208

150(2)

71073

Monoclinic

P21n

12370(3) pm

148433(14) pm

188725(19) pm

90059(8)deg

96311(14)deg

90082(13)deg

34442(10)

2

1304

1892

1416

030 x 025 x 015

292 to 2500deg

-14lt=hlt=14

-15lt=klt=17

-14lt=llt=22

17371

6032 [R(int) = 00487]

995

Analytical

0807 and 0584


6032 2 364

0911

R1 = 00424 wR2 = 00801

R1 = 00874 wR2 = 00885

0497 and -0457

Appendix

- 143 -


Compound 6 8 12

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C46 H65 Ge2 N3

80519

150(2)

71073

Monoclinic

C2c

44536(2) pm

98204(5) pm

218135(10) pm

90deg

116030(4)deg

90deg

85727(7)

8

1248

1436

3408

038 x 024 x 010

305 to 2500deg

-49lt=hlt=52

-10lt=klt=11

-24lt=llt=25

20162

7493 [R(int) = 00954]

992


100000 and 074676


7493 0 476

0917

R1 = 00559 wR2 = 00778

R1 = 01461 wR2 = 00966

0590 and -0578

C46 H65 Ge N3 Sn

85129

150(2)

71073

Triclinic

P-1

867780(10) pm

120514(4) pm

210797(6) pm

96333(2)deg

97393(2)deg

99141(2)deg

213908(10)

2

1322

1320

888

016 x 014 x 012

295 to 2500deg

-10lt=hlt=10

-14lt=klt=14

-25lt=llt=25

16936

7496 [R(int) = 00251]

994


100000 and 099037


7496 0 495

1001

R1 = 00309 wR2 = 00706

R1 = 00437 wR2 = 00733

1468 and -0424

C37 H48 N2

52077

150(2)

71073

Triclinic

P-1

108485(5) pm

127284(7) pm

132348(4) pm

65748(4)deg

86290(3)deg

71699(5)deg

157759(12)

2

1096

0063

568

029 x 022 x 018

298 to 2500deg

-11lt=hlt=12

-15lt=klt=15

-15lt=llt=15

13428

5541 [R(int) = 00203]

998

None

09888 and 09820


5541 0 364

1029

R1 = 00439 wR2 = 00900

R1 = 00633 wR2 = 00963

0188 and -0193

Appendix

- 144 -


Compound 14 16 17

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C37 H46 Cl Ge N2

62680

150(2)

71073

Monoclinic

P21c

117621(2) pm

175495(4) pm

166051(3) pm

90deg

107053(2)deg

90deg

327691(11)

4

1270

1044

1324

040 x 032 x 022

342 to 2500deg

-13lt=hlt=13

-19lt=klt=20

-19lt=llt=18

16923

5742 [R(int) = 00250]

997


100000 and 082078


5742 0 378

1044

R1 = 00328 wR2 = 00709

R1 = 00496 wR2 = 00742

0736 and -0362

C37 H46 Ge N2

59135

150(2)

71073

Triclinic

P-1

108388(6) pm

127885(7) pm

132778(4) pm

66971(4)deg

85749(3)deg

71833(5)deg

160695(13)

2

1222

0980

628

029 x 015 x 007

307 to 2500deg

-12lt=hlt=12

-15lt=klt=15

-15lt=llt=15

13501

5636 [R(int) = 00366]

996


100000 and 092510


5636 0 369

1031

R1 = 00489 wR2 = 01180

R1 = 00691 wR2 = 01242

0539 and -0501

C37 H49 Ge N3

60838

150(2)

71073

Monoclinic

P21c

117714(4) pm

174309(6) pm

166868(6) pm

90deg

106866(4)deg

90deg

32766(2)

4

1233

0964

1296

030 x 023 x 019

342 to 2500deg

-8lt=hlt=13

-10lt=klt=20

-19lt=llt=16

12816

5749 [R(int) = 00325]

998


100000 and 095425


5749 0 378

1060

R1 = 00464 wR2 = 01084

R1 = 00699 wR2 = 01133

1717 and -0738

Appendix

- 145 -


Compound 18 20 22

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C37 H48 Ge N2 O

60936

150(2)

71073

Monoclinic

P21c

117560(3) pm

174116(5) pm

166421(4) pm

90deg

106992(3)deg

90deg

325778(15)

4

1242

0971

1296

031 x 014 x 005

343 to 2500deg

-13lt=hlt=13

-20lt=klt=20

-19lt=llt=19

23624

5720 [R(int) = 00371]

998


100000 and 083390


5720 0 379

1018

R1 = 00336 wR2 = 00752

R1 = 00516 wR2 = 00789

0521 and -0366

C28 H38 N2

40260

150(2)

71073

Monoclinic

P21c

94924(4) pm

256583(9) pm

107465(5) pm

90deg

110403(5)deg

90deg

245320(18)

4

1090

0063

880

017 x 015 x 013

343 to 2500deg

-11lt=hlt=10

-30lt=klt=27

-12lt=llt=11

8561

4313 [R(int) = 00209]

997


100000 and 099057


4313 0 281

1041

R1 = 00476 wR2 = 01015

R1 = 00771 wR2 = 01083

0253 and -0194

C28 H37 Cl Ge N2 O

52564

150(2)

71073

Triclinic

P-1

89021(3) pm

107319(4) pm

151176(6) pm

75734(4)deg

74781(3)deg

75311(3)deg

132282(8)

2

1320

1281

552

020 x 012 x 008

354 to 2500deg

-10lt=hlt=10

-12lt=klt=12

-15lt=llt=17

9246

4654 [R(int) = 00211]

997


100000 and 086160


4654 0 304

0946

R1 = 00274 wR2 = 00579

R1 = 00386 wR2 = 00597

0394 and -0264

Appendix

- 146 -


Compound 23 27 28

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C28 H36 Cl2 Ge N2

54408

150(2)

71073

Monoclinic

C2c

279616(13) pm

113538(3) pm

177729(7) pm

90deg

109718(5)deg

90deg

53115(4)

8

1361

1374

2272

021 x 017 x 015

332 to 2500deg

-25lt=hlt=33

-7lt=klt=13

-21lt=llt=20

10951

4663 [R(int) = 00459]

997


100000 and 091223


4663 0 304

0856

R1 = 00372 wR2 = 00584

R1 = 00684 wR2 = 00620

0589 and -0533


60780

150(2)

71073

Monoclinic

P21c

121593(5) pm

162045(6) pm

171248(7) pm

90deg

98177(4)deg

90deg

33399(2)

4

1209

0295

1304

030 x 015 x 005

335 to 2500deg

-14lt=hlt=13

-16lt=klt=19

-20lt=llt=20

23741

5865 [R(int) = 00491]

998


100000 and 086688


5865 172 490

1035

R1 = 00543 wR2 = 01080

R1 = 00905 wR2 = 01194

0310 and -0412

C30 H46 N4 O Si2

53489

150(2)

71073

Orthorhombic

Fdd2

31188(2) pm

39120(3) pm

102620(6) pm

90deg

90deg

90deg

125204(14)

16

1135

0141

4640

031 x 011 x 007

334 to 2500deg

-28lt=hlt=36

-46lt=klt=45

-12lt=llt=12

11517

4372 [R(int) = 00656]

997


100000 and 097469


4372 1 346

0897

R1 = 00488 wR2 = 00604

R1 = 00754 wR2 = 00650

0328 and -0229

Appendix

- 147 -


Compound 29 30 31

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C38 H58 N4 Ni O Si2

70177

150(2)

71073

Triclinic

P-1

98776(8) pm

129530(11) pm

155488(13) pm

81634(7)deg

83316(7)deg

82826(7)deg

19430(3)

2

1200

0594

756

020 x 009 x 007

330 to 2500deg

-11lt=hlt=11

-15lt=klt=13

-18lt=llt=18

14961

6828 [R(int) = 00414]

997


100000 and 091998


6828 0 474

0948

R1 = 00386 wR2 = 00807

R1 = 00605 wR2 = 00853

0407 and -0240

C21 H41 N2 P Si3

43680

173(2)

71073

Orthorhombic

Pbca

193556(7) pm

142399(4) pm

199777(6) pm

90deg

90deg

90deg

55063(3)

8

1054

0239

1904

039 x 036 x 016

351 to 2500deg

-13lt=hlt=23

-16lt=klt=16

-23lt=llt=22

19912

4836 [R(int) = 00961]

998


09627 and 09125


4836 18 287

0906

R1 = 00571 wR2 = 00889

R1 = 01270 wR2 = 01032

0316 and -0214

C44 H60 N4 P2 Si2

76308

173(2)

71073

Monoclinic

C2c

23841(3) pm

101993(12) pm

19369(2) pm

90deg

108346(12)deg

90deg

44703(9)

4

1134

0184

1640

076 x 057 x 055

353 to 2500deg

-28lt=hlt=28

-12lt=klt=12

-20lt=llt=23

16197

3927 [R(int) = 00447]

997


09053 and 08725


3927 0 251

1034

R1 = 00618 wR2 = 01393

R1 = 00843 wR2 = 01489

0721 and -0649

Appendix

- 148 -



Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)


140312

150(2)

71073

Triclinic

P-1

105159(4) pm

127622(6) pm

269391(12) pm

90310(4)deg

90855(3)deg

102927(3)deg

35232(3)

2

1323

1000

1456

013 x 012 x 009

336 to 2500deg

-12lt=hlt=12

-15lt=klt=15

-29lt=llt=32

25757

12396 [R(int) = 00546]

997


09154 and 08810


12396 536 816

2077

R1 = 01231 wR2 = 01906

R1 = 01495 wR2 = 01944

1510 and -4753

C91 H139 N8 O4 Pd Si4

162786

150(2)

71073

Triclinic

P-1

145970(8) pm

151441(15) pm

232982(16) pm

71358(8)deg

74666(5)deg

85365(6)deg

47063(6)

2

1149

0298

1750

019 x 013 x 011

327 to 2500deg

-17lt=hlt=17

-17lt=klt=18

-27lt=llt=27

41022

16531 [R(int) = 00735]

998


09679 and 09455


16531 284 1112

0908

R1 = 00558 wR2 = 01021

R1 = 01075 wR2 = 01128

0688 and -0448

C40 H54 Fe Ge2 N4

79190

150(2)

71073

Monoclinic

P21n

10532(3) pm

20258(5) pm

18990(5) pm

90deg

10542(3)deg

90deg

39060(19)

4

1347

1927

1648

012 x 008 x 005

322 to 2500deg

-6lt=hlt=12

-22lt=klt=24

-22lt=llt=21

16887

6870 [R(int) = 01353]

997


100000 and 073478


6870 213 498

1044

R1 = 00912 wR2 = 01786

R1 = 01680 wR2 = 02282

0570 and -1404

Appendix

- 149 -



Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C40 H54 Fe Ge2 N4

79190

150(2)

71073

Monoclinic

P21n

165582(11) pm

127695(7) pm

198175(12) pm

90deg

107428(7)deg

90deg

39979(4)

4

1316

1883

1648

012 x 011 x 009

337 to 2499deg

-16lt=hlt=19

-15lt=klt=15

-23lt=llt=23

29049

7015 [R(int) = 00329]

998


100000 and 052405


7015 0 436

1065

R1 = 00263 wR2 = 00574

R1 = 00318 wR2 = 00595

0357 and -0360


82692

150(2)

71073

Monoclinic

P21c

119176(7) pm

160794(9) pm

220424(13) pm

90deg

94402(5)deg

90deg

42115(4)

4

1304

0831

1752

015 x 013 x 007

323 to 2500deg

-14lt=hlt=14

-19lt=klt=17

-16lt=llt=26

17786

7404 [R(int) = 01111]

998


100000 and 075122


7404 0 490

1052

R1 = 00717 wR2 = 01045

R1 = 01208 wR2 = 01181

0467 and -0370


91592

150(2)

71073

Monoclinic

P21c

121662(3) pm

160596(3) pm

220073(5) pm

90deg

93549(2)deg

90deg

429163(16)

4

1418

2134

1896

015 x 011 x 008

336 to 2500deg

-14lt=hlt=14

-19lt=klt=19

-26lt=llt=26

33743

7539 [R(int) = 00521]

998


100000 and 068509


7539 0 521

1259

R1 = 00400 wR2 = 00965

R1 = 00536 wR2 = 01000

0376 and -0373

Appendix

- 150 -


following tables



2times10

3)


x y z U(eq)

N(1) 1159(1) 1176(1) 6836(1) 20(1)

C(1) 1706(2) 1650(1) 6995(1) 21(1)

N(2) -1293(2) 1547(1) 7057(1) 23(1)

C(2) 789(2) 2089(1) 7078(1) 20(1)

C(3) -626(2) 2021(1) 7158(1) 20(1)

C(4) 3331(2) 1741(1) 7112(2) 29(1)

C(5) 3920(2) 2283(1) 7590(2) 34(1)

C(6) 2795(2) 2681(1) 6772(2) 35(1)

C(7) 1375(2) 2643(1) 7102(2) 27(1)

C(8) -1522(2) 2482(1) 7295(2) 21(1)

C(9) -2759(2) 2643(1) 6227(2) 27(1)

C(10) -3571(2) 3077(1) 6331(2) 33(1)

C(11) -3169(2) 3358(1) 7498(2) 35(1)

C(12) -1948(2) 3199(1) 8573(2) 32(1)

C(13) -1133(2) 2765(1) 8467(2) 27(1)

C(14) -2537(2) 1417(1) 7503(2) 35(1)

C(15) -3250(3) 920(1) 6823(2) 61(1)

C(16) -1974(3) 1344(1) 9002(2) 65(1)

C(17) 2080(2) 741(1) 6834(2) 20(1)

C(18) 2353(2) 597(1) 5670(2) 23(1)

C(19) 3237(2) 160(1) 5724(2) 29(1)

C(20) 3821(2) -131(1) 6867(2) 32(1)

C(21) 3480(2) -1(1) 7977(2) 29(1)

C(22) 2598(2) 427(1) 7984(2) 23(1)

C(23) 2150(2) 562(1) 9174(2) 28(1)

C(24) 2101(2) 91(1) 10028(2) 39(1)

C(25) 3156(2) 987(1) 10029(2) 42(1)

C(26) 1602(2) 885(1) 4374(2) 29(1)

C(27) 2645(3) 974(1) 3586(2) 53(1)

C(28) 195(3) 588(1) 3539(2) 54(1)

Appendix

- 151 -


2times10

3)


x y z U(eq)

Ge(1) 4751(1) 5279(1) 3913(1) 24(1)

Cl(1) 4863(1) 7474(1) 3443(1) 35(1)

O(1) 2591(1) 5468(1) 4187(1) 20(1)

N(1) 4469(2) 5098(1) 2623(1) 17(1)

C(1) 3006(2) 5278(2) 2582(1) 16(1)

N(2) 1482(2) 7765(2) 2375(1) 20(1)

C(2) 2432(2) 5062(2) 1801(1) 21(1)

C(3) 1144(2) 4228(2) 2174(2) 31(1)

C(4) -158(2) 4793(2) 2933(2) 30(1)

C(5) 534(2) 4844(2) 3741(1) 21(1)

C(6) 1810(2) 5684(2) 3440(1) 17(1)

C(7) 1063(2) 7152(2) 3205(1) 18(1)

C(8) 820(2) 9172(2) 2096(1) 26(1)

C(9) 397(3) 9344(2) 1159(2) 40(1)

C(10) 2058(3) 9950(2) 2035(2) 43(1)

C(11) -95(2) 7719(2) 3998(1) 18(1)

C(12) 434(2) 8108(2) 4652(1) 22(1)

C(13) -648(2) 8637(2) 5376(1) 27(1)

C(14) -2259(2) 8769(2) 5459(2) 30(1)

C(15) -2795(2) 8370(2) 4815(2) 30(1)

C(16) -1724(2) 7845(2) 4085(1) 24(1)

C(17) 5786(2) 4690(2) 1889(1) 19(1)

C(18) 6546(2) 3361(2) 1997(1) 22(1)

C(19) 7868(2) 3005(2) 1310(2) 28(1)

C(20) 8423(2) 3902(2) 552(2) 29(1)

C(21) 7656(2) 5209(2) 464(1) 26(1)

C(22) 6329(2) 5635(2) 1128(1) 21(1)

C(23) 5549(2) 7085(2) 991(2) 26(1)

C(24) 6701(3) 7932(2) 989(2) 41(1)

C(25) 4931(3) 7520(2) 84(2) 40(1)

C(26) 6001(2) 2315(2) 2820(2) 27(1)

C(27) 5775(3) 1139(2) 2495(2) 40(1)

C(28) 7175(3) 1863(2) 3471(2) 38(1)

Appendix

- 152 -


2times10

3)


x y z U(eq)

Ge(1) 967(1) 7605(1) 1823(1) 18(1)

Cl(1) 1020(1) 9314(1) 2345(1) 29(1)

N(1) 1401(1) 6550(2) 2449(1) 19(1)

C(1) 1534(1) 5601(2) 2029(2) 16(1)

Cl(2) 198(1) 7116(1) 1640(1) 31(1)

N(2) 1101(1) 7630(2) 909(1) 15(1)

C(2) 1548(1) 5691(2) 1285(2) 15(1)

C(3) 1442(1) 6764(2) 777(2) 14(1)

C(4) 1615(1) 6867(2) 172(2) 19(1)

C(5) 1945(1) 5989(2) -42(2) 26(1)

C(6) 2098(1) 4966(2) 547(2) 22(1)

C(7) 1669(1) 4652(2) 844(2) 21(1)

C(8) 1625(1) 4444(2) 2470(2) 17(1)

C(9) 1229(1) 3875(2) 2611(2) 23(1)

C(10) 1291(1) 2785(2) 2983(2) 29(1)

C(11) 1764(2) 2263(3) 3232(2) 32(1)

C(12) 2169(1) 2832(3) 3121(2) 30(1)

C(13) 2101(1) 3920(2) 2737(2) 22(1)

C(14) 1621(1) 6630(2) 3327(2) 20(1)

C(15) 1219(1) 6848(3) 3699(2) 32(1)

C(16) 2052(1) 7524(2) 3583(2) 34(1)

C(17) 833(1) 8395(2) 248(2) 17(1)

C(18) 1019(1) 9542(2) 207(2) 19(1)

C(19) 745(1) 10248(3) -431(2) 29(1)

C(20) 315(1) 9844(3) -1011(2) 36(1)

C(21) 147(1) 8718(3) -973(2) 33(1)

C(22) 399(1) 7960(2) -350(2) 20(1)

C(23) 215(1) 6700(2) -377(2) 23(1)

C(24) 329(1) 6020(3) -1045(2) 34(1)

C(25) -341(1) 6612(3) -475(2) 31(1)

C(26) 1517(1) 10001(2) 789(2) 22(1)

C(27) 1914(1) 10083(3) 375(2) 32(1)

C(28) 1463(1) 11198(2) 1144(2) 36(1)

Appendix

- 153 -


2times10

3)


x y z U(eq)

Sn(1) 4689(1) 4918(1) 3222(1) 24(1)

Sn(2) 5822(1) 5994(1) 1674(1) 30(1)

Cl(1) 4488(3) 6215(2) 3883(1) 38(1)

Cl(2) 3266(2) 3378(2) 3638(1) 39(1)

Cl(3) 7188(2) 7769(2) 1449(1) 43(1)

Cl(4) 6104(3) 5090(3) 888(1) 57(1)

Si(1) 6825(2) 4259(2) 3587(1) 17(1)

Si(2) 8610(3) 6420(2) 3531(1) 28(1)

Si(3) 9814(2) 4466(2) 3664(1) 26(1)

Si(4) 3648(2) 6680(2) 1375(1) 21(1)

Si(5) 1981(3) 4463(2) 1299(1) 30(1)

Si(6) 649(3) 6348(2) 1247(1) 30(1)

N(1) 6586(7) 2924(5) 3299(3) 20(2)

N(2) 6484(6) 3264(5) 4080(3) 16(2)

N(3) 8389(7) 5001(5) 3582(3) 23(2)

N(4) 3751(7) 7937(6) 1722(3) 22(2)

N(5) 3959(8) 7800(6) 936(3) 27(2)

N(6) 2102(7) 5865(6) 1329(3) 24(2)

C(1) 6258(8) 2470(7) 3742(4) 24(2)

C(2) 5630(8) 1296(7) 3832(3) 20(2)

C(3) 4328(9) 879(7) 3742(4) 30(2)

C(4) 3826(11) -209(8) 3826(4) 44(3)

C(5) 4613(12) -855(8) 3977(4) 47(3)

C(6) 5921(13) -450(9) 4064(4) 54(3)

C(7) 6446(10) 640(8) 3992(4) 36(3)

C(8) 6469(9) 2487(7) 2787(3) 22(2)

C(9) 7183(11) 3385(8) 2465(4) 43(3)

C(10) 5041(10) 2180(9) 2612(4) 44(3)

C(11) 7093(12) 1524(8) 2741(4) 49(3)

C(12) 6251(9) 3286(8) 4625(3) 26(2)

C(13) 4851(10) 2720(9) 4759(4) 48(3)

C(14) 7218(10) 2783(8) 4908(4) 39(3)

C(15) 6455(10) 4474(7) 4759(4) 31(2)

C(16) 7585(10) 6750(8) 3014(4) 43(3)

C(17) 8192(11) 7005(8) 4123(4) 44(3)

C(18) 10317(10) 7108(8) 3367(5) 55(4)

C(19) 10809(9) 4684(9) 3087(4) 39(3)

C(20) 9461(9) 3008(7) 3775(4) 30(2)

Appendix

- 154 -

C(21) 10726(10) 5062(9) 4232(4) 41(3)

C(22) 4144(9) 8514(7) 1315(3) 22(2)

C(23) 4603(10) 9700(7) 1286(3) 30(2)

C(24) 5918(10) 10173(8) 1332(4) 36(3)

C(25) 6315(12) 11289(9) 1292(4) 46(3)

C(26) 5453(14) 11926(9) 1203(4) 50(3)

C(27) 4158(14) 11457(9) 1158(4) 52(3)

C(28) 3726(12) 10336(8) 1194(4) 41(3)

C(29) 3829(9) 8261(7) 2260(3) 24(2)

C(30) 3041(13) 9101(10) 2358(4) 65(4)

C(31) 3223(10) 7251(8) 2537(4) 41(3)

C(32) 5223(10) 8649(10) 2438(4) 59(4)

C(33) 4252(10) 7910(8) 398(3) 30(2)

C(34) 3489(13) 8669(11) 158(4) 67(4)

C(35) 3812(13) 6813(9) 170(4) 60(4)

C(36) 5705(11) 8321(11) 315(4) 63(4)

C(37) 3040(11) 4003(8) 1778(4) 49(3)

C(38) 2431(11) 4059(8) 669(4) 44(3)

C(39) 310(10) 3713(8) 1447(5) 48(3)

C(40) -433(9) 5964(9) 1795(4) 43(3)

C(41) 921(10) 7835(9) 1209(4) 48(3)

C(42) -186(11) 5795(10) 650(4) 57(4)

C(43) -180(17) 209(14) 3445(7) 59(3)

C(44) -1099(17) -417(14) 3132(7) 58(3)

C(45) -949(16) -322(14) 2634(7) 58(2)

C(46) 75(15) 387(13) 2440(7) 58(2)

C(47) 979(17) 1008(14) 2750(6) 60(2)

C(48) 829(17) 908(15) 3251(7) 60(3)

C(49) 210(20) 473(17) 1887(7) 58(3)

C(43A) 798(17) 917(14) 2044(7) 58(3)

C(44A) 1381(17) 1418(14) 2465(7) 59(3)

C(45A) 931(16) 1088(14) 2929(7) 59(3)

C(46A) -134(15) 231(13) 2969(7) 58(2)

C(47A) -748(17) -263(14) 2547(6) 58(2)

C(48A) -289(17) 75(14) 2084(7) 58(2)

C(49A) -640(20) -111(17) 3469(8) 60(3)

C(50) 120(20) -463(18) -179(10) 106(6)

C(51) -640(30) -620(20) 236(10) 106(6)

C(52) -730(20) 250(20) 530(10) 107(6)

C(53) -70(30) 1260(20) 404(11) 109(6)

C(54) 680(20) 1409(19) -10(11) 107(6)

C(55) 780(30) 558(19) -303(11) 106(6)

C(56) 250(30) -1390(20) -499(12) 120(7)

Appendix

- 155 -

C(57) 575(16) 499(14) 4873(6) 52(3)

C(58) 807(18) -512(14) 4941(8) 53(3)

C(59) -138(17) -1326(14) 5128(7) 55(3)

C(60) -1333(18) -1140(15) 5253(8) 57(3)

C(61) -1572(16) -130(15) 5187(7) 56(3)

C(62) -620(17) 686(15) 5000(8) 53(3)

C(63) 1600(20) 1369(17) 4669(9) 59(5)

Appendix

- 156 -









palladium





Chem Eur J 2011 17 4890-4895



Matthias Driess















Appendix

- 157 -

75 Curriculum Vitae

Personal Data



Nationality Chinese

Education




Bachelor Chemistry










appropriately cited

Wenyuan Wang

Berlin Juli 2012

Table of contents

iii

6 REFERENCES 129

7 APPENDIX 138






Introduction

- 1 -

1 INTRODUCTION






effect[1]













is maximal[4]










Introduction

- 2 -














silanone I3[9]









elements[11]



Introduction

- 3 -








The


Very




The bonding


0 donor-



bonds of ns2rarrp


orbitals[3 12d]





Introduction

- 4 -















and






Ge single[13f]






Introduction

- 5 -


reported by







order of three










species[12c]









(Scheme 16)



Introduction

- 6 -










II



The



[29]) was reported




II and Pb






this work

Introduction

- 7 -










SiIV







With these new





Introduction

- 8 -










The donor














Introduction

- 9 -







I23 with a Si0=Si




I





I











Introduction

- 10 -

I28[40]











reagents[43]


with a Ge0=Ge

0













Introduction

- 11 -






Jambor showed that








compound I32











Introduction

- 12 -




and I41[50]







minus) Nevertheless












synthetic chemists




Surprisingly X-ray



was









Introduction

- 13 -



















Introduction

- 14 -













II halides (ArE





Wright 1997


I52 Lappert 1997

SnNMe2

Sn

Me2N

NR

NR

NN

SiMe3

E

(Me3Si)2N

E

Me3Si

N(SiMe3)2

N

N

SiMe3

Sn

(Me3Si)2N

Sn

Me3Si

N(SiMe3)2

Lappert 1994


NN

N N

SnSn

SiMe3

SiMe3

Me3Si

Me3Si

I53 Lappert 1997

NN

N N

SnSn

SiMe3

SiMe3

Me3Si

Me3Si

Sn

Sn

Power 2005

I56 E = Ge R = Dip

I57 E = Sn R = Tip

R

RE

NH2

E

H2N

R

R








Introduction

- 15 -





and with





germylene I63[64]





(I65-I74) were






(aLSi-O-Si

aL

aL = PhC(

tBuN)2


Introduction

- 16 -


I77[68]


and









II Pb

II like I79

were presented[69]











Introduction

- 17 -






while







shown in detail















State of

Development


Introduction

- 18 -






and bis-stannylenes

















Introduction

- 19 -



prepared[74]






donor groups[72 76]
















Introduction

- 20 -


have received more






Motivation

- 21 -

2 MOTIVATION


























Motivation

- 22 -












- 23 -







and

(nacnac)GeCl3 2[82]




germanium derivates




derivative 3[83]




(nacnac)Ge-NH-



spectroscopy (1H


analyses



- 24 -












1H- and














but









- 25 -














35728(7) N1-C4 1382(3) C1-C2 1516(3) C2-C3 1411(3) C3-C4 1371(3)

C4-C5 1508(3) C2-Ge1-N1 843(1) C4-N1-Ge1 1130(1) C3-C2-C1 1202(2)

C3-C2-Ge1 1116(2) C1-C2-Ge1 1281(2) C4-C3-C2 1174(2) C3-C4-N1

1135(2) C3-C4-C5 1254(2)






- 26 -












1905(2) N1-C2 1329(3) N2-C4 1332(3) C1-C2 1518(3) C2-C3 1394(3)

C3-C4 1394(3) C4-C5 1512(3) N3-Ge1-N1 9720(8) N3-Ge1-N2 8876(9)


1227(2) C4-C3-C2 1269(3) N2-C4-C3 1239(3)


- 27 -























- 28 -








have been


species 5[83]











have been











- 29 -




and longer
















Ge2rsquo 1184(3) N2-C4-C3 1220(3)


cluster 5 The




- 30 -






cluster






- 31 -








compounds[93]







correlation[96]


The


approximation)[98]


potential



IGLO program[99]


theory[100]

The B3LYP[96a 101]


quality were









- 32 -































- 33 -














σ-character






150 pm abovea)


200 pm abovea)






a)



- 34 -


ring)
























- 35 -








(I27


I bonds










13C









- 36 -








ppm in the 119







The new GeI-Ge



I example Their







I


(257-








- 37 -

















Ge2 2549(1) Ge1-N1 2015(4) Ge1-N2 2038(4) Ge2-N3 1951(4) Ge2-C31

1903(5) N1-Ge1-N2 8867(15) N1-Ge1-Ge2 10430(11) N2-Ge1-Ge2


- 38 -

10149(12) C31-Ge2-N3 8447(19) C31-Ge2-Ge1 11890(15) N3-Ge2-Ge1


N3 1964(2) Ge1-C31 1915(3) N2-Sn1-N1 8288(8) N2-Sn1-Ge1 9542(5)


Ge1-Sn1 10200(6)


















- 39 -


I dimers






- 1206

LUMO

- 3911

HOMO

- 1138

LUMO

- 4024

HOMO

E [eV]

6a 8a

- 1206

LUMO

- 3911

HOMO

- 1138

LUMO

- 4024

HOMO

E [eV]

6a 8a















- 40 -







products[81-83 109]





benzenamine 9[111]




or (Z)-N-isopropyl








- 41 -

Et2O - 78degCnBuLi

Et2O - 78degCN

Dip

9

N

Dip

10

Li

N

Ph Dip

Cl

11

12

N

NH

Ph

Dip

Dip

Et2O - 78degC

N

Ph iPr

Cl

19

20

NH

N

Ph

Dip

iPr













respectively








- 42 -

N1C1

C2

C3 N2

Ph Dip

Dip

N1C1

C2

C3 N2

Ph iPr

Dip

1356

1386

1445

1309

1377

1360

1305

1452

12 20

HH





C13 14349(18) C1-C2 13769(19) C1-C4 15136(18) N2-C3 13046(16) N2-

C25 14297(17) C2-C3 14515(18) C2-C7 15257(18) N1-C1-C2 12221(12)

C1-C2-C3 12230(12) N2-C3-C2 12212(12) For 20 N1-C1 1309(2) N1-C17

1418(2) C1-C2 1445(2) C1-C4 1522(2) N2-C3 1356(2) N2-C14 1461(2)

C2-C3 1386(2) C2-C7 1524(2) C3-C8 1495(2) N1-C1-C2 12080(15) C1-

C2-C3 12151(15) N2-C3-C2 12288(15)






complex[27]



- 43 -























- 44 -



















published in 2006




22956(7) N1-C1 1342(3) N1-C14 1458(3) C1-C2 1397(3) C1-C8 1502(3)

N2-C3 1333(3) N2-C26 1463(2) C2-C3 1415(3) C2-C7 1522(3) C3-C4


- 45 -

1509(3) C4-C5 1522(3) N1-Ge1-N2 9123(7) N1-Ge1-Cl1 9560(5) N2-Ge1-

Cl1 9392(5) C1-N1-Ge1 12568(13) N1-C1-C2 12352(17) C1-C2-C3

12503(19) N2-C3-C2 12440(18) C3-N2-Ge1 12515(13)




N1-C8 1442(4) N2-C1 1408(4) N2-C20 1454(4) C1-C2 1359(4) C2-C3

1461(4) C1-C32 1498(4) C2-C7 1525(4) C3-C4 1360(4) N1-Ge1-N2

9509(11) C3-N1-Ge1 300(2) N1-C3-C2 1176(3) C1-C2-C3 1267(3) C2-C1-

N2 1241(3) C1-N2-Ge1 1259(2)











- 46 -











The 1H- and









154 ppm)[114]





and 3308 cmndash1


)[115]



- 47 -

= 3643 cmndash1




)[114]









due to the





[114]




N2 2017(2) Ge1-N3 1829(3) N1-C1 1349(4) C1-C2 1395(4) N2-C3

1336(4) C2-C3 1417(4) C3-C4 1509(4) N3-Ge1-N2 9503(11) N3-Ge1-N1

9709(13) N2-Ge1-N1 8932(10) C1-N1-Ge1 1253(2) C3-N2-Ge1 1247(2)

For 18 Ge1-O1 18249(18) Ge1-N2 20054(17) Ge1-N1 20071(16) N1-C1


- 48 -

1340(3) C1-C2 1402(3) N2-C3 1331(3) C2-C3 1419(3) C3-C4 1509(3)


12597(14) C3-N2-Ge1 12515(14)
















- 49 -









23 respectively














In compound 23 GeIV



center are





of the GeIV



- 50 -










Ge1-O1 18265(12) Ge1-N1 20908(15) O1-C6 1418(2) N1-C1 1284(2) N2-

C7 1272(2) C1-C6 1525(2) C6-C7 1539(2) Cl1-Ge1-O1 9789(4) Cl1-Ge1-

N1 9422(4) O1-Ge1-N1 8158(6) Ge1-N1-C1 11291(12) N1-C1-C6

11484(16) C1-C6-O1 10975(14) C6-O1-Ge1 11838(10) N2-C7-C6

11778(17) For 23 Ge1-Cl1 21339(7) Ge1-Cl2 21375(9) Ge1-N1 1798(2)

Ge1-N2 1788(2) N1-C1 1430(3) C1-C2 1339(4) C2-C3 1486(4) C3-C4

1326(4) N2-C3 1441(3) N2-Ge1-N1 10554(10) N2-Ge1-Cl1 11208(7) N1-


10276(3) C1-C2-C3 1266(2) C4-C3-N2 1209(2) C2-C4-C3 1208(3)





- 51 -







IIL [E = Si Ge Sn X











(aLSi-O-Si

aL

aL = PhC(


silylene I24[37]

(aLSi-Si




in








- 52 -





in 53 yield




in 76 yield The





tBu groups at δ =



Si-NMR spectrum of


- 53 -








aLSiO

iPr) (δ = -

135 ppm)[31b]

respectively


















package[101c 119]






The


- 54 -



(Figure 313)




20349(16) Cl2-Si2 22017(11) Si2-O1 1581(8) Si2-N3 1798(2) Si2-N4

1968(2) Si1-O1 1562(8) Si1-N2 1750(10) Si1-N1 1994(6) Si1-O1-Si2

1680(6)




1652(2) Si1-N1 1896(3) Si1-N2 1902(3) Si2-N3 1888(2) Si2-N4 1908(3)


N3 10196(11) O1-Si2-N4 10481(12) N1-Si1-N2 6815(10) N3-Si2-N4

6855(11)


- 55 -








29[32a]








- 56 -



















2216(2) pm][120]


(21395(8) pm)[121]









(2130-2146 pm)[121]





- 57 -

29

[Si][Si]

O

Ni

[Si] [Si]

Ni

CO CO

[Si] [Si]

Ni

N N tButBu

Si

N N DipDip

Si

[Si] = [Si] =

29a 29b

2207 2216

2191 2197689deg

934deg

1084deg 1019deg

1708 1701

2139 2139





Si1-N1 18929(19) Si1-N2 1875(2) Si2-O1 17081(17) Si2-N3 18776(19)


6941(9) N3-Si2-N4 6954(8)







- 58 -


Phosphasilene













oligomerize[126c]















- 59 -


aLSiCl



aL) 31






was easily


26[31a]





The 29





[31b] One





ppm)[31b]


- 60 -







aLSi-P




iPr2 derivative

[31b] The Si1-P1


pm) in the aLSi-P



subunit






- 61 -


10854(8)












72 yield





tBu






P-NMR spectrum



- 62 -








Phosphasilene[128]





(tBu3Si)2SiSi(Si














N2-Si1-N1 7078(11) P1-Si1-P1rsquo 10766(4)


- 63 -



















aLSiCl (1870(2) pm and 1917(2) pm)





- 64 -


















silylene 30 (0920)




- 65 -




























The


- 66 -




(Scheme 327)




















- 67 -





(Scheme 329) The



Si-N






(right)




N1 1832(7) Si1-N2 1827(7) Si1-N3 1705(7) Si2-N3 1780(7) Si3-N3



1248(4) Si2-N3-Si3 1179(4)


- 68 -















I58[61]

and

I64[65]










- 69 -












compound 35[33b]



13C-

and 29









- 70 -


singlet in the 29



tBu

iPr)

[31b]






31G(d)][101c 119]











(R = tBu

iPr)



- 71 -






by theoretical

calculation






O2-C3 13028


complex 36






36[33b]


(Scheme 333)


- 72 -













IV atom Si1 and the









complex[72b 77 135]




- 73 -


-Pd













23038(11) Si1-O1 1694(3) Si1-N1 1789(4) Si2-O2 1675(3) Si2-N5 1862(3)



Si2Si1

C1

Pd

Si3

213 pm

233 pm236 pm

230 pm

O1 O2


- 74 -

7861(11) Si2-Pd1-C1 7681(11) Si3-Pd1-C1 16783(12)


tBu groups









The 29



complexes[71 137]





The



)[135c 135f 136a]









335


- 75 -
















minus1


donor than PIII





minus1


- 76 -



and the first bis-






aLSi-Fc-Si


aLGe-Fc-Ge



PhD thesis[33a]









quantitatively














- 77 -






Si-NMR spectrum










The GeII centers






tBuC(N-Dip)2)




bidentate ligand


- 78 -




1979(9) Ge(2)-C(7) 1983(11) Ge(1)-N(1) 2027(8) Ge(1)-N(2) 2006(8)

Ge(2)-N(3) 2022(7) Ge(2)-N(4) 2037(7) C(1)-Ge(1)-N(2) 983(3) C(1)-Ge(1)-

N(1) 955(3) N(2)-Ge(1)-N(1) 653(3) C(7)-Ge(2)-N(3) 953(4) C(7)-Ge(2)-


Ge2-C8 19774(19) Ge1-N1 20261(16) Ge1-N2 20247(17) Ge2-N3

20402(15) Ge2-N4 20162(16) C1-Ge1-N1 9662(7) C1-Ge1-N2 9445(7) N1-


6459(6)




(Figure 323)


- 79 -







ferrocene molecules

6 9 0 6 9 5 7 0 0 7 0 5 7 1 0 7 1 5 7 2 0

m z

0

1 0

2 0

3 0

4 0

5 0

6 0

7 0

8 0

9 0

1 0 0

0

1 0

2 0

3 0

4 0

5 0

6 0

7 0

8 0

9 0

1 0 0

Re

lative

Abu

nda

nce

7 0 3 3 2 9

7 0 4 3 3 2

7 0 5 3 3 47 0 1 3 3 4

7 0 6 3 2 96 9 0 2 4 9 6 9 5 2 2 5 7 1 7 3 4 57 1 0 4 7 3

7 0 3 3 3 1

7 0 4 3 3 4

7 0 5 3 3 87 0 1 3 3 6

7 0 6 3 3 17 1 0 3 3 5

N L 3 1 3 E 7


N L 4 9 7 E 5


p a C hrg 1





- 80 -


recently[139]






transition-metals




0[32a


complex I65-Mo[66b]



[140] was





I

complex 41[33a]


42[33a]




- 81 -











42 δ = 699 737 and 891 ppm) In the 29













complex 41a[141]



[142] (21348(5) pm)


[143] (2228(2) pm) in


[141] (22060(6) and 22017(6) pm)






- 82 -





21252(14) Co1-Si2 21200(14) Si1-C6 1894(5) Si2-C11 1887(5) Si1-N1


9389(5) N1-Si1-N2 6847(15) N3-Si2-N4 6866(16) C6-Si1-Co1 13254(14)



- 83 -

C11 1961(4) Ge1-N1 2020(3) Ge1-N2 2031(3) Ge2-N3 2041(3) Ge2-N4

2029(3) Ge1-Co1-Ge2 9279(2) N1-Ge1-N2 6490(11) N3-Ge2-N4 6485(11)

C6-Ge1-Co1 13280(10) C11-Ge2-Co1 13140(10)



(2262(1) pm) and


4-((


and 25036(3) pm)[90d]


















- 84 -


tBu groups at δ =





of 41 In the 13






(ν = 1968 cmminus1

)[141]










tBu groups at δ =



Si-



- 85 -



C-



tBuO)SirarrFe(CO)4





)[71]
















2)-C(sp

3) coupling




- 86 -




expected[148]




Thus the catalytic


(Scheme 342)








- 87 -














- 88 -














Summary

- 89 -









in 33 yield








with KC8


in very low yield


dianion (CBD2-


core

Summary

- 90 -



and





in










Summary

- 91 -








was obtained by








in high yield










activation

Summary

- 92 -














[32a]



Summary

- 93 -







silylene 30[128]




product 31[128]










Summary

- 94 -









by 13-dilithium



as orange




SiIV




Summary

- 95 -











furnished





CoI complex 41


I complex 42

[33a]


Summary

- 96 -



are not shown












2)-C(sp

3)

cross-coupling[147]



Summary

- 97 -


probed[148-150]






- 98 -


51 General section




















dichloromethane





- 99 -









1H 400 MHz

13C


Si-NMR spectra were



The 1H and

13C








119Sn

1H external SnMe4








)












- 100 -






peak)























- 101 -










tBu [152]



9 (C5H10)C=N-Dip [111] 39 aLGeCl [41]



- 102 -











(030 g 083 mmol 33)





1H NMR (40013 MHz THF-D8 298K) δ = 108 (d

3JHH = 7 Hz 6 H




13C





378 Found C 5764 H 694 N 367




- 103 -

mmol 31)

NHN

GeN

Dip

DipDip

C41H59GeN3 MW 66657



1H NMR (40013 MHz C6D6 298K) δ = 091 (d

3JHH = 68 Hz 6 H


3JHH =





13C




C NCMe)

EI-MS mz () 6674 (03 [M]+) 4912 (100 [M -

iPr2C6H3NH]

+)


C 7354 H 868 N 613














- 104 -






C66H100Ge4K2N4O2 MW 135028


Found C 7821 H 999 N 281


C46H65Ge2N3 MW 80531








017 mmol 66)




- 105 -

1H NMR (40013 MHz C6D6 298K) δ = 107 (d

3JHH = 7 Hz 12 H


3JHH = 7




3JHH = 7 Hz 2 H



arom H)

13C






NCMe)





C 6884 H 800 N 516










- 106 -



dark red crystals



1H NMR (40013 MHz C6D6 298K) δ = 085 (d

3JHH = 7 Hz 6 H


3JHH = 7


3JHH = 7 Hz 6 H CHMe2) 129 (d




3JHH



721 (m 9 H arom H)

13C






NCMe)

119Sn NMR

(C6D6) δ = -197

UV-vis λ [nm] = 314 (15000) 363 (14500) 541 (2800)




Found C 6444 H 764 N 477


- 107 -


C37H48N2 MW 52079














1H NMR (40013 MHz CDCl3 298K) δ = 117 (d

3JHH = 7 Hz 6 H


3JHH = 7




arom H)

13C





CN) 1658 (Ph-CN)



8518 H 927 N 547


- 108 -


N

N

Ph

Dip

Dip

Cl

Ge












1H NMR (40013 MHz C6D6 298K) δ = 097 (d

3JHH = 7 Hz 3 H


3JHH = 7

Hz 3 H CHMe2) 121-127 (m 9 H CHMe2) 128-139 (m




3JHH = 7 Hz 1 H



13C





295 (Cy-CH2) 315 (Cy-CH2) 1089 (Cy-CCN) 1234-1476

(arom C) 1651 (Cy-CN) 1688 (Ph-CN)



Found C 7073 H 762 N 457


- 109 -


C37H46GeN2 MW 59142


ylidene 15[113]









1H NMR (40013 MHz C6D6 298K) δ = 115 (d

3JHH = 7 Hz 6 H


3JHH = 7




3JHH =

44 Hz 1 H C=CH) 675- 725 (m 11 H arom H)

13C




1117 (Cy-CCN) 1236-1431 (arom C) 1473 1474 (Cy-CN

Ph-CN)

IR (KBr cm-1

) 704 (s) 787 (s) 939 (m) 1104 (s) 1135 (s) 1204 (s) 1248 (s)

1296 (s) 1322 (s) 1365 (s) 1439 (s) 1461 (s) 1535 (m) 1600

(s) 2822 (m) 2865 (s) 2922 (s) 2957 (w) 3022 (w) 3061 (m)



C 7495 H 800 N 484


- 110 -


C37H49GeN3 MW 60845








1H NMR (40013 MHz C6D6 298K) δ = 106 (d

3JHH = 7 Hz 3 H



154 (s 2 H NH2) 200-213 (m 4 H Cy-CH2) 346 (sept


3JHH = 7 Hz 1 H



13C





293 (Cy-CH2) 315 (Cy-CH2) 1023 (Cy-CCN) 1234-1462

(arom C) 1643 (Cy-CN) 1669 (Ph-CN)

IR (KBr cm-1

) 561 (s) 704 (s) 752 (s) 796 (s) 839 (m) 922 (s) 1096 (s)

1143 (s) 1174 (s) 1252 (s) 1304 (s) 1360 (s) 1430 (s) 1543

(s) 2865 (m) 2961 (s) 3021 (w) 3048 (m) 3343 (w) 3430

(w)


C 7272 H 810 N 683


- 111 -










1H NMR (40013 MHz C6D6 298K) δ = 111 (d

3JHH = 7 Hz 3 H



166 (s 1 H OH) 195-221 (m 4 H Cy-CH2) 335 (sept


3JHH = 7 Hz 1 H



13C





291 (Cy-CH2) 314 (Cy-CH2) 1028 (Cy-CCN) 1233-1464

(arom C) 1647 (Cy-CN) 1666 (Ph-CN)

IR(KBr cm-1

) 561 (s) 713 (s) 743 (s) 770 (s) 791 (s) 839 (s) 926 (m)

1056 (m) 1104 (s) 1148 (s) 1170 (s) 1257 (s) 1313 (s) 1339

(s) 1365 (s) 1430 (s) 1470 (s) 1539 (s) 2861 (s) 2961 (s)

3018 (w) 3057 (m) 3643 (m)




- 112 -

Found C 7300 H 786 N 464


C28H38N2 MW 40230













1H NMR (40013 MHz CDCl3 298K) δ = 109 (d

3JHH = 7 Hz 6 H


3JHH = 7




1203 (d 3JHH = 7 Hz 1 H NH)

13C




(Cy-CCN) 1226 1228 1275 1282 1284 1371 1389

1453 (arom C) 1576 (Cy-CN) 1673 (PhCN)



- 113 -


8270 H 977 N 679













1H NMR (40013 MHz C6D6 298K) δ = 106 (d

3JHH = 7 Hz 3 H


3JHH = 7






3JHH = 7 Hz


1 H arom H) 705-724 (m 7 H arom H)

13C





- 114 -

293 (Cy-CH2) 312 (Cy-CH2) 537 (CHMe2) 1068 (Cy-

CCN) 1239 1250 1267 1271 1288 1294 1388 1410

1446 1469 (arom C) 1620 (Cy-CN) 1654 (Ph-CN)


Found C 6426 H 725 N 551










287 mmol 57 )



1H NMR (40013 MHz C6D6 298K) δ = 113 (d

3JHH = 7 Hz 6 H


3JHH = 7




3JHH =

42 Hz 1 H C=CH) 701-726 (m 8 H arom H)

13C


CH2) 247 (CHMe2) 254 (Cy-CH2) 257 (CHMe2) 286


- 115 -


1125 (Cy-CCN) 1248 1287 1296 1354 1391 1411

1421 1490 (arom C) 1682 (Cy-CN) 1709 (Ph-CN)


Found C 6203 H 517 N 679




tBu













(s 2 H SiHCl) 733- 746 (m 10 H arom H)

13C


1276 1285 1297 1337 (arom C) 1711 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = -1110

IR(KBr cm-1

) 606 (s) 658 (m) 711 (s) 733 (s) 760 (s) 789 (s) 934 (s)

1068 (s) 1200 (s) 1269 (s) 1378 (s) 1486 (s) 1550 (s) 1566

(s) 1612 (s) 1783 (w) 1826 (w) 1950 (w) 1969 (w) 2000


- 116 -

(w) 2135 (s) 2188 (s) 2909 (s) 2934 (s) 2971 (s) 3232 (m)



Found C 5971 H 797 N 913


C30H46N4OSi2 MW 53488










731(m 10 H arom H)

13C


1277 1291 1299 1349 (arom C) 1623 (NCN)

29Si

1H NMR (7949 MHz C6D6 298K) δ = -161

IR(KBr cm-1

) 608 (s) 709 (s) 746 (s) 790 (s) 892 (m) 972 (s) 1032 (m)

1070 (m) 1208 (s) 1268 (m) 1359 (s) 1412 (s) 1446 (s)

1476 (s) 1577 (m) 1648 (m) 1778 (w) 1826 (w) 1899 (w)

1970 (w) 2248 (w) 2867 (s) 2902 (s) 2928 (s) 2964 (s)

3065 (m)


- 117 -



Found C 6688 H 857 N 1046












(m 4 H CH2) 295 (m 4 H CH2) 504 (s 4 H =CH) 686-

707 (m 10 H arom H)

13C


(CMe3) 760 (=CH) 1277 1293 1296 1335 (arom C)

1690 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = 328

IR(KBr cm-1

) 607 (s) 644 (s) 698 (s) 750 (s) 792 (s) 925 (m) 1021 (m)

1075 (s) 1209 (s) 1267 (s) 1320 (m) 1361 (s) 1407 (s)

1444 (s) 1475 (s) 1578 (m) 1647 (m) 1775 (w) 1823 (w)


- 118 -

1902 (w) 1962 (w) 2280 (w) 2791 (s) 2855 (s) 2913 (s)

2975 (s) 3023 (m) 3063 (w)



Found C 6387 H 837 N 805


C21H41N2PSi3 MW 43679


(302 mg 102





085 mmol 83)



1H NMR (40013 MHz C6D6 298K) δ = 058 (d

3JP-H = 44 Hz 18 H


734-741 (m 3 H arom H)

13C

1H NMR (10061 MHz C6D6 298K) δ = 44 (d

3JC-P = 100 Hz


1292 1293 1344 (arom C) 1572 (d 3JC-P = 95 Hz

NCN)

29Si

1H NMR (7949 MHz C6D6 298K) δ = 31 (d

1JSi-P = 229 Hz


31P NMR (81012 MHz C6D6 298K) δ = - 2110


- 119 -



C30H46N4P2Si2 MW 58083





mg 025 mmol 72)




733 (m 10 H arom H)

13C


(CMe3) 1256 1276 1294 1359 (arom C) 1710 (NCN)

29Si

1H NMR (7949 MHz THF-D8 298K) δ = 267 (t

1JSi-P = 998 Hz)

31P NMR (81012 MHz THF-D8 298K) δ = - 1649


5802361


- 120 -




(336 mg 114










689 Found C 4195 H 701 N 706


C44H66N4O2Si2 MW 73919









- 121 -





174 (s 18 H ArC(CH3)3) 693 - 713 (m 8 H arom H) 754


13C


(NC(CH3)3) 350 (ArC(CH3)3) 530 (NC(CH3)3) 1096

1243 1276 1295 1297 1313 1341 1552 (arom C)

1636 (NCN)

29Si

1H NMR (7949 MHz C6D6 298K) δ = -240


Found C 7075 H 930 N 756


C88H132N8O4PdSi4 MW 158480








- 122 -






(s 9 H C(CH3)3) 114 (s 9 H C(CH3)3) 116 (s 9 H

C(CH3)3) 131 (s 9 H C(CH3)3) 139 (s 9 H C(CH3)3)155

(s 9 H C(CH3)3) 168 (s 9 H C(CH3)3) 177 (s 9 H

C(CH3)3) 180 (s 9 H C(CH3)3) 185 (s 9 H C(CH3)3) 212

(s 9 H C(CH3)3) 659 (s 1 H SiH) 686- 789 (m 22 H


13C

1H NMR (10061 MHz C6D6 298K) δ = 309 (C(CH3)3) 311

(C(CH3)3) 314 (C(CH3)3) 316 (C(CH3)3) 318 (C(CH3)3)

319 (C(CH3)3) 320 (C(CH3)3) 322 (C(CH3)3) 328

(C(CH3)3) 332 (C(CH3)3) 333 (C(CH3)3) 343 (C(CH3)3)

349 350 351 357 526 527 537 539 540 541 542

561 1112 1225 1236 1243 1256 1258 1271 1285

1287 1289 1291 1293 1294 1302 1303 1318 1323

1324 1326 1340 1342 1378 1380 1381 1409 1430

1533 1559 1585 1613 1622 1654 1731 1742

29Si


658 (LSiPd)

IR(KBr cm-1

) 623 (m) 706 (m) 764 (m) 860 (m) 1056 (m) 1108 (m) 1206

(m) 1272 (m) 1365 (m) 1418 (s) 1446 (m) 1476 (m) 1446

(m) 1476 (m) 1495 (m) 1591 (m) 2135 (w) 2875(m) 2906

(s) 2964 (s) 3061 (w)


707 Found C 6616 H 875 N 676


- 123 -















451 (t 3JHH = 15 Hz 4 H FeCH) 472 (t

3JHH = 15 Hz 4 H

FeCH) 692- 707 (m 10 H arom H)

13C



1294 1305 1349 (arom C) 1604 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = 433



Found C 6803 H 767 N 778


- 124 -















(t 3JHH = 16 Hz 4 H FeCH) 471 (t

3JHH = 16 Hz 4 H


H)

13C



1290 1302 1369 (arom C) 1659 (NCN)


C 6655 H 701 N 707


- 125 -


tBu

N

N

tBu

PhSi

tBu

N

N

tBu

Ph Si

Co

Fe













440 (t 3JHH = 16 Hz 4 H FeCH) 461 (t

3JHH = 16 Hz 4 H


692- 696 (m 6 H arom H) 720- 723 (m 2 H arom H)

13C



(SiC) 1291 1297 1300 1343 (arom C) 1673 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = 820



Found C 6612 H 724 N 686


- 126 -


tBu

N

N

tBu

PhGe

tBu

N

N

tBu

Ph Ge

Co

Fe













438 (t 3JHH = 15 Hz 4 H FeCH) 459 (t

3JHH = 15 Hz 4 H


695- 698 (m 6 H arom H) 714- 718 (m 2 H arom H)

13C



(GeC) 1287 1296 1300 1361(arom C) 1680 (NCN)


Found C 5942 H 664 N 590


- 127 -











461 (m 4 H FeCH) 476 (m 4 H FeCH) 523 (s 10 H

CoCH) 683- 695 (m 6 H arom H) 702- 706 (m 2 H

arom H) 745- 748 (m 2 H arom H)

13C



(CoCH) 1287 1296 1300 1324 (arom C) 1687 (NCN)

2078 (br CO)

29Si

1H NMR (7949 MHz C6D6 298K) δ = 857

IR(KBr cm-1

) 500 (m) 539 (w) 564 (m) 628 (s) 703 (m) 757 (s) 792 (m)

825 (w) 1028 (m) 1081 (w) 1146 (m) 1199 (s) 1275 (m)

1360 (m) 1388 (m) 1417 (s) 1438 (w) 1474 (m) 1520 (s)

1641 (s) 1888 (s) 2869 (s) 2901 (m) 2926 (m) 2965 (s)

1520 (s) 3097 (w)



- 128 -

556 Found C 6287 H 630 N 571


C48H54Fe3N4O8Si2 MW 103867










H) 736- 739 (m 2 H arom H)

13C



1287 1303 1308 (arom C) 1704 (NCN) 2169 (CO)

29Si

1H NMR (7949 MHz C6D6 298K) δ = 1050

IR(KBr cm-1

) 630 (s) 765 (w) 1028 (m) 1035 (m) 1200 (m) 1370 (w)

1400 (m) 1474 (w) 1609 (w) 1648 (w) 1900 (s) 1948 (s)

1996(w) 2026 (s) 2865 (w) 2930 (m) 2965 (m)


539 Found C 5623 H 517 N 566

References

- 129 -

6 REFERENCES



353


3877












2010 16 436


1955 77 884











Chem Int Ed 2003 42 2222




Chem Soc 1994 116 3667







References

- 130 -










5683













11366


Science 2008 321 1069




12315











9701




References

- 131 -

2008 47 1650






121 347







Int Ed 2011 50 5374


1991 1302


2004 630 2090



4130


1994 33 1156


Int Ed 1997 36 261


Inorg Chem 1997 36 5202



2008 130 12268



127 17530











References

- 132 -


















2012 51 399


5058















2011 44 588









References

- 133 -










20 1190



Allg Chem 2001 627 836




Soc 1996 118 10457





3655






Soc 2011 133 5103



Soc 1996 118 6317


Chem Rev 2005 105 3842










Phys 2000 2 2137

References

- 134 -



Phys Rev 1988 37 785









Chem Soc 2006 128 1023










2005 127 3516


2004 43 1419



2343




2003 pp 2217













References

- 135 -



CT 2004
























2868

















References

- 136 -












Chem Int Ed 2007 46 4141



2009 82 793







Chem 2011 50 8502




1804

















7162

References

- 137 -




Appendix

- 138 -

7 APPENDIX

71 Abbreviations



mmol millimole(ar)





















Et ethyl t triplet







IR infrared

K Kelvin


functions aL PhC(

tBuN)2








Appendix

- 139 -

GeN

N

GeN

Dip

Dip

DipCl

N

SnN

Dip

Dip

GeNN

SnN

Dip

DipDip

N

Dip

6 7


1 2 3 4

5 8 9

10 11 12 13 14

15 16 17 18

19 20 21 22

Appendix

- 140 -

23 24 25 26

27 28 29

30 31 32 33

34 35 36

tBu

N

N

tBu

Ph

Si

Cl

37 38 39 40

Appendix

- 141 -

tBu

N

N

tBu

PhSi

tBu

N

N

tBu

Ph Si

Co

Fe

41 42 43

44 45 46

47a 47b 48a 48b

Appendix

- 142 -



Compound 3 4 5

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C50 H88 Ge2 K2 N2 O4

100460

150(2)

71073

Triclinic

P-1

106989(7) pm

114137(7) pm

122625(8) pm

74158(6) deg

76395(6) deg

83400(5) deg

139807(16)

1

1193

1263

536

028 x 02 x 018

326 to 2500deg

-12lt=hlt=12

-13lt=klt=13

-14lt=llt=14

12268

4910 [R(int) = 00358]

996


100000 and 094847


4910 0 281

0940

R1 = 00328 wR2 = 00638

R1 = 00538 wR2 = 00666

0456 and -0223

C41 H5 Ge N3

66650

150(2)

71073

Triclinic

P-1

91129(6) pm

113531(7) pm

190282(10) pm

100360(5) deg

101854(5) deg

98627(5) deg

185918(19)

2

1191

0855

716

039 x 012 x 007

297 to 2500deg

-10lt=hlt=10

-13lt=klt=13

-22lt=llt=22

14570

6543 [R(int) = 00560]

998


0943 and 0777


6543 0 420

0785

R1 = 00399 wR2 = 00513

R1 = 00853 wR2 = 00566

0577 and -0317

C66 H102 Ge4 K2 N4 O2

135208

150(2)

71073

Monoclinic

P21n

12370(3) pm

148433(14) pm

188725(19) pm

90059(8)deg

96311(14)deg

90082(13)deg

34442(10)

2

1304

1892

1416

030 x 025 x 015

292 to 2500deg

-14lt=hlt=14

-15lt=klt=17

-14lt=llt=22

17371

6032 [R(int) = 00487]

995

Analytical

0807 and 0584


6032 2 364

0911

R1 = 00424 wR2 = 00801

R1 = 00874 wR2 = 00885

0497 and -0457

Appendix

- 143 -


Compound 6 8 12

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C46 H65 Ge2 N3

80519

150(2)

71073

Monoclinic

C2c

44536(2) pm

98204(5) pm

218135(10) pm

90deg

116030(4)deg

90deg

85727(7)

8

1248

1436

3408

038 x 024 x 010

305 to 2500deg

-49lt=hlt=52

-10lt=klt=11

-24lt=llt=25

20162

7493 [R(int) = 00954]

992


100000 and 074676


7493 0 476

0917

R1 = 00559 wR2 = 00778

R1 = 01461 wR2 = 00966

0590 and -0578

C46 H65 Ge N3 Sn

85129

150(2)

71073

Triclinic

P-1

867780(10) pm

120514(4) pm

210797(6) pm

96333(2)deg

97393(2)deg

99141(2)deg

213908(10)

2

1322

1320

888

016 x 014 x 012

295 to 2500deg

-10lt=hlt=10

-14lt=klt=14

-25lt=llt=25

16936

7496 [R(int) = 00251]

994


100000 and 099037


7496 0 495

1001

R1 = 00309 wR2 = 00706

R1 = 00437 wR2 = 00733

1468 and -0424

C37 H48 N2

52077

150(2)

71073

Triclinic

P-1

108485(5) pm

127284(7) pm

132348(4) pm

65748(4)deg

86290(3)deg

71699(5)deg

157759(12)

2

1096

0063

568

029 x 022 x 018

298 to 2500deg

-11lt=hlt=12

-15lt=klt=15

-15lt=llt=15

13428

5541 [R(int) = 00203]

998

None

09888 and 09820


5541 0 364

1029

R1 = 00439 wR2 = 00900

R1 = 00633 wR2 = 00963

0188 and -0193

Appendix

- 144 -


Compound 14 16 17

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C37 H46 Cl Ge N2

62680

150(2)

71073

Monoclinic

P21c

117621(2) pm

175495(4) pm

166051(3) pm

90deg

107053(2)deg

90deg

327691(11)

4

1270

1044

1324

040 x 032 x 022

342 to 2500deg

-13lt=hlt=13

-19lt=klt=20

-19lt=llt=18

16923

5742 [R(int) = 00250]

997


100000 and 082078


5742 0 378

1044

R1 = 00328 wR2 = 00709

R1 = 00496 wR2 = 00742

0736 and -0362

C37 H46 Ge N2

59135

150(2)

71073

Triclinic

P-1

108388(6) pm

127885(7) pm

132778(4) pm

66971(4)deg

85749(3)deg

71833(5)deg

160695(13)

2

1222

0980

628

029 x 015 x 007

307 to 2500deg

-12lt=hlt=12

-15lt=klt=15

-15lt=llt=15

13501

5636 [R(int) = 00366]

996


100000 and 092510


5636 0 369

1031

R1 = 00489 wR2 = 01180

R1 = 00691 wR2 = 01242

0539 and -0501

C37 H49 Ge N3

60838

150(2)

71073

Monoclinic

P21c

117714(4) pm

174309(6) pm

166868(6) pm

90deg

106866(4)deg

90deg

32766(2)

4

1233

0964

1296

030 x 023 x 019

342 to 2500deg

-8lt=hlt=13

-10lt=klt=20

-19lt=llt=16

12816

5749 [R(int) = 00325]

998


100000 and 095425


5749 0 378

1060

R1 = 00464 wR2 = 01084

R1 = 00699 wR2 = 01133

1717 and -0738

Appendix

- 145 -


Compound 18 20 22

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C37 H48 Ge N2 O

60936

150(2)

71073

Monoclinic

P21c

117560(3) pm

174116(5) pm

166421(4) pm

90deg

106992(3)deg

90deg

325778(15)

4

1242

0971

1296

031 x 014 x 005

343 to 2500deg

-13lt=hlt=13

-20lt=klt=20

-19lt=llt=19

23624

5720 [R(int) = 00371]

998


100000 and 083390


5720 0 379

1018

R1 = 00336 wR2 = 00752

R1 = 00516 wR2 = 00789

0521 and -0366

C28 H38 N2

40260

150(2)

71073

Monoclinic

P21c

94924(4) pm

256583(9) pm

107465(5) pm

90deg

110403(5)deg

90deg

245320(18)

4

1090

0063

880

017 x 015 x 013

343 to 2500deg

-11lt=hlt=10

-30lt=klt=27

-12lt=llt=11

8561

4313 [R(int) = 00209]

997


100000 and 099057


4313 0 281

1041

R1 = 00476 wR2 = 01015

R1 = 00771 wR2 = 01083

0253 and -0194

C28 H37 Cl Ge N2 O

52564

150(2)

71073

Triclinic

P-1

89021(3) pm

107319(4) pm

151176(6) pm

75734(4)deg

74781(3)deg

75311(3)deg

132282(8)

2

1320

1281

552

020 x 012 x 008

354 to 2500deg

-10lt=hlt=10

-12lt=klt=12

-15lt=llt=17

9246

4654 [R(int) = 00211]

997


100000 and 086160


4654 0 304

0946

R1 = 00274 wR2 = 00579

R1 = 00386 wR2 = 00597

0394 and -0264

Appendix

- 146 -


Compound 23 27 28

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C28 H36 Cl2 Ge N2

54408

150(2)

71073

Monoclinic

C2c

279616(13) pm

113538(3) pm

177729(7) pm

90deg

109718(5)deg

90deg

53115(4)

8

1361

1374

2272

021 x 017 x 015

332 to 2500deg

-25lt=hlt=33

-7lt=klt=13

-21lt=llt=20

10951

4663 [R(int) = 00459]

997


100000 and 091223


4663 0 304

0856

R1 = 00372 wR2 = 00584

R1 = 00684 wR2 = 00620

0589 and -0533


60780

150(2)

71073

Monoclinic

P21c

121593(5) pm

162045(6) pm

171248(7) pm

90deg

98177(4)deg

90deg

33399(2)

4

1209

0295

1304

030 x 015 x 005

335 to 2500deg

-14lt=hlt=13

-16lt=klt=19

-20lt=llt=20

23741

5865 [R(int) = 00491]

998


100000 and 086688


5865 172 490

1035

R1 = 00543 wR2 = 01080

R1 = 00905 wR2 = 01194

0310 and -0412

C30 H46 N4 O Si2

53489

150(2)

71073

Orthorhombic

Fdd2

31188(2) pm

39120(3) pm

102620(6) pm

90deg

90deg

90deg

125204(14)

16

1135

0141

4640

031 x 011 x 007

334 to 2500deg

-28lt=hlt=36

-46lt=klt=45

-12lt=llt=12

11517

4372 [R(int) = 00656]

997


100000 and 097469


4372 1 346

0897

R1 = 00488 wR2 = 00604

R1 = 00754 wR2 = 00650

0328 and -0229

Appendix

- 147 -


Compound 29 30 31

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C38 H58 N4 Ni O Si2

70177

150(2)

71073

Triclinic

P-1

98776(8) pm

129530(11) pm

155488(13) pm

81634(7)deg

83316(7)deg

82826(7)deg

19430(3)

2

1200

0594

756

020 x 009 x 007

330 to 2500deg

-11lt=hlt=11

-15lt=klt=13

-18lt=llt=18

14961

6828 [R(int) = 00414]

997


100000 and 091998


6828 0 474

0948

R1 = 00386 wR2 = 00807

R1 = 00605 wR2 = 00853

0407 and -0240

C21 H41 N2 P Si3

43680

173(2)

71073

Orthorhombic

Pbca

193556(7) pm

142399(4) pm

199777(6) pm

90deg

90deg

90deg

55063(3)

8

1054

0239

1904

039 x 036 x 016

351 to 2500deg

-13lt=hlt=23

-16lt=klt=16

-23lt=llt=22

19912

4836 [R(int) = 00961]

998


09627 and 09125


4836 18 287

0906

R1 = 00571 wR2 = 00889

R1 = 01270 wR2 = 01032

0316 and -0214

C44 H60 N4 P2 Si2

76308

173(2)

71073

Monoclinic

C2c

23841(3) pm

101993(12) pm

19369(2) pm

90deg

108346(12)deg

90deg

44703(9)

4

1134

0184

1640

076 x 057 x 055

353 to 2500deg

-28lt=hlt=28

-12lt=klt=12

-20lt=llt=23

16197

3927 [R(int) = 00447]

997


09053 and 08725


3927 0 251

1034

R1 = 00618 wR2 = 01393

R1 = 00843 wR2 = 01489

0721 and -0649

Appendix

- 148 -



Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)


140312

150(2)

71073

Triclinic

P-1

105159(4) pm

127622(6) pm

269391(12) pm

90310(4)deg

90855(3)deg

102927(3)deg

35232(3)

2

1323

1000

1456

013 x 012 x 009

336 to 2500deg

-12lt=hlt=12

-15lt=klt=15

-29lt=llt=32

25757

12396 [R(int) = 00546]

997


09154 and 08810


12396 536 816

2077

R1 = 01231 wR2 = 01906

R1 = 01495 wR2 = 01944

1510 and -4753

C91 H139 N8 O4 Pd Si4

162786

150(2)

71073

Triclinic

P-1

145970(8) pm

151441(15) pm

232982(16) pm

71358(8)deg

74666(5)deg

85365(6)deg

47063(6)

2

1149

0298

1750

019 x 013 x 011

327 to 2500deg

-17lt=hlt=17

-17lt=klt=18

-27lt=llt=27

41022

16531 [R(int) = 00735]

998


09679 and 09455


16531 284 1112

0908

R1 = 00558 wR2 = 01021

R1 = 01075 wR2 = 01128

0688 and -0448

C40 H54 Fe Ge2 N4

79190

150(2)

71073

Monoclinic

P21n

10532(3) pm

20258(5) pm

18990(5) pm

90deg

10542(3)deg

90deg

39060(19)

4

1347

1927

1648

012 x 008 x 005

322 to 2500deg

-6lt=hlt=12

-22lt=klt=24

-22lt=llt=21

16887

6870 [R(int) = 01353]

997


100000 and 073478


6870 213 498

1044

R1 = 00912 wR2 = 01786

R1 = 01680 wR2 = 02282

0570 and -1404

Appendix

- 149 -



Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C40 H54 Fe Ge2 N4

79190

150(2)

71073

Monoclinic

P21n

165582(11) pm

127695(7) pm

198175(12) pm

90deg

107428(7)deg

90deg

39979(4)

4

1316

1883

1648

012 x 011 x 009

337 to 2499deg

-16lt=hlt=19

-15lt=klt=15

-23lt=llt=23

29049

7015 [R(int) = 00329]

998


100000 and 052405


7015 0 436

1065

R1 = 00263 wR2 = 00574

R1 = 00318 wR2 = 00595

0357 and -0360


82692

150(2)

71073

Monoclinic

P21c

119176(7) pm

160794(9) pm

220424(13) pm

90deg

94402(5)deg

90deg

42115(4)

4

1304

0831

1752

015 x 013 x 007

323 to 2500deg

-14lt=hlt=14

-19lt=klt=17

-16lt=llt=26

17786

7404 [R(int) = 01111]

998


100000 and 075122


7404 0 490

1052

R1 = 00717 wR2 = 01045

R1 = 01208 wR2 = 01181

0467 and -0370


91592

150(2)

71073

Monoclinic

P21c

121662(3) pm

160596(3) pm

220073(5) pm

90deg

93549(2)deg

90deg

429163(16)

4

1418

2134

1896

015 x 011 x 008

336 to 2500deg

-14lt=hlt=14

-19lt=klt=19

-26lt=llt=26

33743

7539 [R(int) = 00521]

998


100000 and 068509


7539 0 521

1259

R1 = 00400 wR2 = 00965

R1 = 00536 wR2 = 01000

0376 and -0373

Appendix

- 150 -


following tables



2times10

3)


x y z U(eq)

N(1) 1159(1) 1176(1) 6836(1) 20(1)

C(1) 1706(2) 1650(1) 6995(1) 21(1)

N(2) -1293(2) 1547(1) 7057(1) 23(1)

C(2) 789(2) 2089(1) 7078(1) 20(1)

C(3) -626(2) 2021(1) 7158(1) 20(1)

C(4) 3331(2) 1741(1) 7112(2) 29(1)

C(5) 3920(2) 2283(1) 7590(2) 34(1)

C(6) 2795(2) 2681(1) 6772(2) 35(1)

C(7) 1375(2) 2643(1) 7102(2) 27(1)

C(8) -1522(2) 2482(1) 7295(2) 21(1)

C(9) -2759(2) 2643(1) 6227(2) 27(1)

C(10) -3571(2) 3077(1) 6331(2) 33(1)

C(11) -3169(2) 3358(1) 7498(2) 35(1)

C(12) -1948(2) 3199(1) 8573(2) 32(1)

C(13) -1133(2) 2765(1) 8467(2) 27(1)

C(14) -2537(2) 1417(1) 7503(2) 35(1)

C(15) -3250(3) 920(1) 6823(2) 61(1)

C(16) -1974(3) 1344(1) 9002(2) 65(1)

C(17) 2080(2) 741(1) 6834(2) 20(1)

C(18) 2353(2) 597(1) 5670(2) 23(1)

C(19) 3237(2) 160(1) 5724(2) 29(1)

C(20) 3821(2) -131(1) 6867(2) 32(1)

C(21) 3480(2) -1(1) 7977(2) 29(1)

C(22) 2598(2) 427(1) 7984(2) 23(1)

C(23) 2150(2) 562(1) 9174(2) 28(1)

C(24) 2101(2) 91(1) 10028(2) 39(1)

C(25) 3156(2) 987(1) 10029(2) 42(1)

C(26) 1602(2) 885(1) 4374(2) 29(1)

C(27) 2645(3) 974(1) 3586(2) 53(1)

C(28) 195(3) 588(1) 3539(2) 54(1)

Appendix

- 151 -


2times10

3)


x y z U(eq)

Ge(1) 4751(1) 5279(1) 3913(1) 24(1)

Cl(1) 4863(1) 7474(1) 3443(1) 35(1)

O(1) 2591(1) 5468(1) 4187(1) 20(1)

N(1) 4469(2) 5098(1) 2623(1) 17(1)

C(1) 3006(2) 5278(2) 2582(1) 16(1)

N(2) 1482(2) 7765(2) 2375(1) 20(1)

C(2) 2432(2) 5062(2) 1801(1) 21(1)

C(3) 1144(2) 4228(2) 2174(2) 31(1)

C(4) -158(2) 4793(2) 2933(2) 30(1)

C(5) 534(2) 4844(2) 3741(1) 21(1)

C(6) 1810(2) 5684(2) 3440(1) 17(1)

C(7) 1063(2) 7152(2) 3205(1) 18(1)

C(8) 820(2) 9172(2) 2096(1) 26(1)

C(9) 397(3) 9344(2) 1159(2) 40(1)

C(10) 2058(3) 9950(2) 2035(2) 43(1)

C(11) -95(2) 7719(2) 3998(1) 18(1)

C(12) 434(2) 8108(2) 4652(1) 22(1)

C(13) -648(2) 8637(2) 5376(1) 27(1)

C(14) -2259(2) 8769(2) 5459(2) 30(1)

C(15) -2795(2) 8370(2) 4815(2) 30(1)

C(16) -1724(2) 7845(2) 4085(1) 24(1)

C(17) 5786(2) 4690(2) 1889(1) 19(1)

C(18) 6546(2) 3361(2) 1997(1) 22(1)

C(19) 7868(2) 3005(2) 1310(2) 28(1)

C(20) 8423(2) 3902(2) 552(2) 29(1)

C(21) 7656(2) 5209(2) 464(1) 26(1)

C(22) 6329(2) 5635(2) 1128(1) 21(1)

C(23) 5549(2) 7085(2) 991(2) 26(1)

C(24) 6701(3) 7932(2) 989(2) 41(1)

C(25) 4931(3) 7520(2) 84(2) 40(1)

C(26) 6001(2) 2315(2) 2820(2) 27(1)

C(27) 5775(3) 1139(2) 2495(2) 40(1)

C(28) 7175(3) 1863(2) 3471(2) 38(1)

Appendix

- 152 -


2times10

3)


x y z U(eq)

Ge(1) 967(1) 7605(1) 1823(1) 18(1)

Cl(1) 1020(1) 9314(1) 2345(1) 29(1)

N(1) 1401(1) 6550(2) 2449(1) 19(1)

C(1) 1534(1) 5601(2) 2029(2) 16(1)

Cl(2) 198(1) 7116(1) 1640(1) 31(1)

N(2) 1101(1) 7630(2) 909(1) 15(1)

C(2) 1548(1) 5691(2) 1285(2) 15(1)

C(3) 1442(1) 6764(2) 777(2) 14(1)

C(4) 1615(1) 6867(2) 172(2) 19(1)

C(5) 1945(1) 5989(2) -42(2) 26(1)

C(6) 2098(1) 4966(2) 547(2) 22(1)

C(7) 1669(1) 4652(2) 844(2) 21(1)

C(8) 1625(1) 4444(2) 2470(2) 17(1)

C(9) 1229(1) 3875(2) 2611(2) 23(1)

C(10) 1291(1) 2785(2) 2983(2) 29(1)

C(11) 1764(2) 2263(3) 3232(2) 32(1)

C(12) 2169(1) 2832(3) 3121(2) 30(1)

C(13) 2101(1) 3920(2) 2737(2) 22(1)

C(14) 1621(1) 6630(2) 3327(2) 20(1)

C(15) 1219(1) 6848(3) 3699(2) 32(1)

C(16) 2052(1) 7524(2) 3583(2) 34(1)

C(17) 833(1) 8395(2) 248(2) 17(1)

C(18) 1019(1) 9542(2) 207(2) 19(1)

C(19) 745(1) 10248(3) -431(2) 29(1)

C(20) 315(1) 9844(3) -1011(2) 36(1)

C(21) 147(1) 8718(3) -973(2) 33(1)

C(22) 399(1) 7960(2) -350(2) 20(1)

C(23) 215(1) 6700(2) -377(2) 23(1)

C(24) 329(1) 6020(3) -1045(2) 34(1)

C(25) -341(1) 6612(3) -475(2) 31(1)

C(26) 1517(1) 10001(2) 789(2) 22(1)

C(27) 1914(1) 10083(3) 375(2) 32(1)

C(28) 1463(1) 11198(2) 1144(2) 36(1)

Appendix

- 153 -


2times10

3)


x y z U(eq)

Sn(1) 4689(1) 4918(1) 3222(1) 24(1)

Sn(2) 5822(1) 5994(1) 1674(1) 30(1)

Cl(1) 4488(3) 6215(2) 3883(1) 38(1)

Cl(2) 3266(2) 3378(2) 3638(1) 39(1)

Cl(3) 7188(2) 7769(2) 1449(1) 43(1)

Cl(4) 6104(3) 5090(3) 888(1) 57(1)

Si(1) 6825(2) 4259(2) 3587(1) 17(1)

Si(2) 8610(3) 6420(2) 3531(1) 28(1)

Si(3) 9814(2) 4466(2) 3664(1) 26(1)

Si(4) 3648(2) 6680(2) 1375(1) 21(1)

Si(5) 1981(3) 4463(2) 1299(1) 30(1)

Si(6) 649(3) 6348(2) 1247(1) 30(1)

N(1) 6586(7) 2924(5) 3299(3) 20(2)

N(2) 6484(6) 3264(5) 4080(3) 16(2)

N(3) 8389(7) 5001(5) 3582(3) 23(2)

N(4) 3751(7) 7937(6) 1722(3) 22(2)

N(5) 3959(8) 7800(6) 936(3) 27(2)

N(6) 2102(7) 5865(6) 1329(3) 24(2)

C(1) 6258(8) 2470(7) 3742(4) 24(2)

C(2) 5630(8) 1296(7) 3832(3) 20(2)

C(3) 4328(9) 879(7) 3742(4) 30(2)

C(4) 3826(11) -209(8) 3826(4) 44(3)

C(5) 4613(12) -855(8) 3977(4) 47(3)

C(6) 5921(13) -450(9) 4064(4) 54(3)

C(7) 6446(10) 640(8) 3992(4) 36(3)

C(8) 6469(9) 2487(7) 2787(3) 22(2)

C(9) 7183(11) 3385(8) 2465(4) 43(3)

C(10) 5041(10) 2180(9) 2612(4) 44(3)

C(11) 7093(12) 1524(8) 2741(4) 49(3)

C(12) 6251(9) 3286(8) 4625(3) 26(2)

C(13) 4851(10) 2720(9) 4759(4) 48(3)

C(14) 7218(10) 2783(8) 4908(4) 39(3)

C(15) 6455(10) 4474(7) 4759(4) 31(2)

C(16) 7585(10) 6750(8) 3014(4) 43(3)

C(17) 8192(11) 7005(8) 4123(4) 44(3)

C(18) 10317(10) 7108(8) 3367(5) 55(4)

C(19) 10809(9) 4684(9) 3087(4) 39(3)

C(20) 9461(9) 3008(7) 3775(4) 30(2)

Appendix

- 154 -

C(21) 10726(10) 5062(9) 4232(4) 41(3)

C(22) 4144(9) 8514(7) 1315(3) 22(2)

C(23) 4603(10) 9700(7) 1286(3) 30(2)

C(24) 5918(10) 10173(8) 1332(4) 36(3)

C(25) 6315(12) 11289(9) 1292(4) 46(3)

C(26) 5453(14) 11926(9) 1203(4) 50(3)

C(27) 4158(14) 11457(9) 1158(4) 52(3)

C(28) 3726(12) 10336(8) 1194(4) 41(3)

C(29) 3829(9) 8261(7) 2260(3) 24(2)

C(30) 3041(13) 9101(10) 2358(4) 65(4)

C(31) 3223(10) 7251(8) 2537(4) 41(3)

C(32) 5223(10) 8649(10) 2438(4) 59(4)

C(33) 4252(10) 7910(8) 398(3) 30(2)

C(34) 3489(13) 8669(11) 158(4) 67(4)

C(35) 3812(13) 6813(9) 170(4) 60(4)

C(36) 5705(11) 8321(11) 315(4) 63(4)

C(37) 3040(11) 4003(8) 1778(4) 49(3)

C(38) 2431(11) 4059(8) 669(4) 44(3)

C(39) 310(10) 3713(8) 1447(5) 48(3)

C(40) -433(9) 5964(9) 1795(4) 43(3)

C(41) 921(10) 7835(9) 1209(4) 48(3)

C(42) -186(11) 5795(10) 650(4) 57(4)

C(43) -180(17) 209(14) 3445(7) 59(3)

C(44) -1099(17) -417(14) 3132(7) 58(3)

C(45) -949(16) -322(14) 2634(7) 58(2)

C(46) 75(15) 387(13) 2440(7) 58(2)

C(47) 979(17) 1008(14) 2750(6) 60(2)

C(48) 829(17) 908(15) 3251(7) 60(3)

C(49) 210(20) 473(17) 1887(7) 58(3)

C(43A) 798(17) 917(14) 2044(7) 58(3)

C(44A) 1381(17) 1418(14) 2465(7) 59(3)

C(45A) 931(16) 1088(14) 2929(7) 59(3)

C(46A) -134(15) 231(13) 2969(7) 58(2)

C(47A) -748(17) -263(14) 2547(6) 58(2)

C(48A) -289(17) 75(14) 2084(7) 58(2)

C(49A) -640(20) -111(17) 3469(8) 60(3)

C(50) 120(20) -463(18) -179(10) 106(6)

C(51) -640(30) -620(20) 236(10) 106(6)

C(52) -730(20) 250(20) 530(10) 107(6)

C(53) -70(30) 1260(20) 404(11) 109(6)

C(54) 680(20) 1409(19) -10(11) 107(6)

C(55) 780(30) 558(19) -303(11) 106(6)

C(56) 250(30) -1390(20) -499(12) 120(7)

Appendix

- 155 -

C(57) 575(16) 499(14) 4873(6) 52(3)

C(58) 807(18) -512(14) 4941(8) 53(3)

C(59) -138(17) -1326(14) 5128(7) 55(3)

C(60) -1333(18) -1140(15) 5253(8) 57(3)

C(61) -1572(16) -130(15) 5187(7) 56(3)

C(62) -620(17) 686(15) 5000(8) 53(3)

C(63) 1600(20) 1369(17) 4669(9) 59(5)

Appendix

- 156 -









palladium





Chem Eur J 2011 17 4890-4895



Matthias Driess















Appendix

- 157 -

75 Curriculum Vitae

Personal Data



Nationality Chinese

Education




Bachelor Chemistry










appropriately cited

Wenyuan Wang

Berlin Juli 2012

Introduction

- 1 -

1 INTRODUCTION






effect[1]













is maximal[4]










Introduction

- 2 -














silanone I3[9]









elements[11]



Introduction

- 3 -








The


Very




The bonding


0 donor-



bonds of ns2rarrp


orbitals[3 12d]





Introduction

- 4 -















and






Ge single[13f]






Introduction

- 5 -


reported by







order of three










species[12c]









(Scheme 16)



Introduction

- 6 -










II



The



[29]) was reported




II and Pb






this work

Introduction

- 7 -










SiIV







With these new





Introduction

- 8 -










The donor














Introduction

- 9 -







I23 with a Si0=Si




I





I











Introduction

- 10 -

I28[40]











reagents[43]


with a Ge0=Ge

0













Introduction

- 11 -






Jambor showed that








compound I32











Introduction

- 12 -




and I41[50]







minus) Nevertheless












synthetic chemists




Surprisingly X-ray



was









Introduction

- 13 -



















Introduction

- 14 -













II halides (ArE





Wright 1997


I52 Lappert 1997

SnNMe2

Sn

Me2N

NR

NR

NN

SiMe3

E

(Me3Si)2N

E

Me3Si

N(SiMe3)2

N

N

SiMe3

Sn

(Me3Si)2N

Sn

Me3Si

N(SiMe3)2

Lappert 1994


NN

N N

SnSn

SiMe3

SiMe3

Me3Si

Me3Si

I53 Lappert 1997

NN

N N

SnSn

SiMe3

SiMe3

Me3Si

Me3Si

Sn

Sn

Power 2005

I56 E = Ge R = Dip

I57 E = Sn R = Tip

R

RE

NH2

E

H2N

R

R








Introduction

- 15 -





and with





germylene I63[64]





(I65-I74) were






(aLSi-O-Si

aL

aL = PhC(

tBuN)2


Introduction

- 16 -


I77[68]


and









II Pb

II like I79

were presented[69]











Introduction

- 17 -






while







shown in detail















State of

Development


Introduction

- 18 -






and bis-stannylenes

















Introduction

- 19 -



prepared[74]






donor groups[72 76]
















Introduction

- 20 -


have received more






Motivation

- 21 -

2 MOTIVATION


























Motivation

- 22 -












- 23 -







and

(nacnac)GeCl3 2[82]




germanium derivates




derivative 3[83]




(nacnac)Ge-NH-



spectroscopy (1H


analyses



- 24 -












1H- and














but









- 25 -














35728(7) N1-C4 1382(3) C1-C2 1516(3) C2-C3 1411(3) C3-C4 1371(3)

C4-C5 1508(3) C2-Ge1-N1 843(1) C4-N1-Ge1 1130(1) C3-C2-C1 1202(2)

C3-C2-Ge1 1116(2) C1-C2-Ge1 1281(2) C4-C3-C2 1174(2) C3-C4-N1

1135(2) C3-C4-C5 1254(2)






- 26 -












1905(2) N1-C2 1329(3) N2-C4 1332(3) C1-C2 1518(3) C2-C3 1394(3)

C3-C4 1394(3) C4-C5 1512(3) N3-Ge1-N1 9720(8) N3-Ge1-N2 8876(9)


1227(2) C4-C3-C2 1269(3) N2-C4-C3 1239(3)


- 27 -























- 28 -








have been


species 5[83]











have been











- 29 -




and longer
















Ge2rsquo 1184(3) N2-C4-C3 1220(3)


cluster 5 The




- 30 -






cluster






- 31 -








compounds[93]







correlation[96]


The


approximation)[98]


potential



IGLO program[99]


theory[100]

The B3LYP[96a 101]


quality were









- 32 -































- 33 -














σ-character






150 pm abovea)


200 pm abovea)






a)



- 34 -


ring)
























- 35 -








(I27


I bonds










13C









- 36 -








ppm in the 119







The new GeI-Ge



I example Their







I


(257-








- 37 -

















Ge2 2549(1) Ge1-N1 2015(4) Ge1-N2 2038(4) Ge2-N3 1951(4) Ge2-C31

1903(5) N1-Ge1-N2 8867(15) N1-Ge1-Ge2 10430(11) N2-Ge1-Ge2


- 38 -

10149(12) C31-Ge2-N3 8447(19) C31-Ge2-Ge1 11890(15) N3-Ge2-Ge1


N3 1964(2) Ge1-C31 1915(3) N2-Sn1-N1 8288(8) N2-Sn1-Ge1 9542(5)


Ge1-Sn1 10200(6)


















- 39 -


I dimers






- 1206

LUMO

- 3911

HOMO

- 1138

LUMO

- 4024

HOMO

E [eV]

6a 8a

- 1206

LUMO

- 3911

HOMO

- 1138

LUMO

- 4024

HOMO

E [eV]

6a 8a















- 40 -







products[81-83 109]





benzenamine 9[111]




or (Z)-N-isopropyl








- 41 -

Et2O - 78degCnBuLi

Et2O - 78degCN

Dip

9

N

Dip

10

Li

N

Ph Dip

Cl

11

12

N

NH

Ph

Dip

Dip

Et2O - 78degC

N

Ph iPr

Cl

19

20

NH

N

Ph

Dip

iPr













respectively








- 42 -

N1C1

C2

C3 N2

Ph Dip

Dip

N1C1

C2

C3 N2

Ph iPr

Dip

1356

1386

1445

1309

1377

1360

1305

1452

12 20

HH





C13 14349(18) C1-C2 13769(19) C1-C4 15136(18) N2-C3 13046(16) N2-

C25 14297(17) C2-C3 14515(18) C2-C7 15257(18) N1-C1-C2 12221(12)

C1-C2-C3 12230(12) N2-C3-C2 12212(12) For 20 N1-C1 1309(2) N1-C17

1418(2) C1-C2 1445(2) C1-C4 1522(2) N2-C3 1356(2) N2-C14 1461(2)

C2-C3 1386(2) C2-C7 1524(2) C3-C8 1495(2) N1-C1-C2 12080(15) C1-

C2-C3 12151(15) N2-C3-C2 12288(15)






complex[27]



- 43 -























- 44 -



















published in 2006




22956(7) N1-C1 1342(3) N1-C14 1458(3) C1-C2 1397(3) C1-C8 1502(3)

N2-C3 1333(3) N2-C26 1463(2) C2-C3 1415(3) C2-C7 1522(3) C3-C4


- 45 -

1509(3) C4-C5 1522(3) N1-Ge1-N2 9123(7) N1-Ge1-Cl1 9560(5) N2-Ge1-

Cl1 9392(5) C1-N1-Ge1 12568(13) N1-C1-C2 12352(17) C1-C2-C3

12503(19) N2-C3-C2 12440(18) C3-N2-Ge1 12515(13)




N1-C8 1442(4) N2-C1 1408(4) N2-C20 1454(4) C1-C2 1359(4) C2-C3

1461(4) C1-C32 1498(4) C2-C7 1525(4) C3-C4 1360(4) N1-Ge1-N2

9509(11) C3-N1-Ge1 300(2) N1-C3-C2 1176(3) C1-C2-C3 1267(3) C2-C1-

N2 1241(3) C1-N2-Ge1 1259(2)











- 46 -











The 1H- and









154 ppm)[114]





and 3308 cmndash1


)[115]



- 47 -

= 3643 cmndash1




)[114]









due to the





[114]




N2 2017(2) Ge1-N3 1829(3) N1-C1 1349(4) C1-C2 1395(4) N2-C3

1336(4) C2-C3 1417(4) C3-C4 1509(4) N3-Ge1-N2 9503(11) N3-Ge1-N1

9709(13) N2-Ge1-N1 8932(10) C1-N1-Ge1 1253(2) C3-N2-Ge1 1247(2)

For 18 Ge1-O1 18249(18) Ge1-N2 20054(17) Ge1-N1 20071(16) N1-C1


- 48 -

1340(3) C1-C2 1402(3) N2-C3 1331(3) C2-C3 1419(3) C3-C4 1509(3)


12597(14) C3-N2-Ge1 12515(14)
















- 49 -









23 respectively














In compound 23 GeIV



center are





of the GeIV



- 50 -










Ge1-O1 18265(12) Ge1-N1 20908(15) O1-C6 1418(2) N1-C1 1284(2) N2-

C7 1272(2) C1-C6 1525(2) C6-C7 1539(2) Cl1-Ge1-O1 9789(4) Cl1-Ge1-

N1 9422(4) O1-Ge1-N1 8158(6) Ge1-N1-C1 11291(12) N1-C1-C6

11484(16) C1-C6-O1 10975(14) C6-O1-Ge1 11838(10) N2-C7-C6

11778(17) For 23 Ge1-Cl1 21339(7) Ge1-Cl2 21375(9) Ge1-N1 1798(2)

Ge1-N2 1788(2) N1-C1 1430(3) C1-C2 1339(4) C2-C3 1486(4) C3-C4

1326(4) N2-C3 1441(3) N2-Ge1-N1 10554(10) N2-Ge1-Cl1 11208(7) N1-


10276(3) C1-C2-C3 1266(2) C4-C3-N2 1209(2) C2-C4-C3 1208(3)





- 51 -







IIL [E = Si Ge Sn X











(aLSi-O-Si

aL

aL = PhC(


silylene I24[37]

(aLSi-Si




in








- 52 -





in 53 yield




in 76 yield The





tBu groups at δ =



Si-NMR spectrum of


- 53 -








aLSiO

iPr) (δ = -

135 ppm)[31b]

respectively


















package[101c 119]






The


- 54 -



(Figure 313)




20349(16) Cl2-Si2 22017(11) Si2-O1 1581(8) Si2-N3 1798(2) Si2-N4

1968(2) Si1-O1 1562(8) Si1-N2 1750(10) Si1-N1 1994(6) Si1-O1-Si2

1680(6)




1652(2) Si1-N1 1896(3) Si1-N2 1902(3) Si2-N3 1888(2) Si2-N4 1908(3)


N3 10196(11) O1-Si2-N4 10481(12) N1-Si1-N2 6815(10) N3-Si2-N4

6855(11)


- 55 -








29[32a]








- 56 -



















2216(2) pm][120]


(21395(8) pm)[121]









(2130-2146 pm)[121]





- 57 -

29

[Si][Si]

O

Ni

[Si] [Si]

Ni

CO CO

[Si] [Si]

Ni

N N tButBu

Si

N N DipDip

Si

[Si] = [Si] =

29a 29b

2207 2216

2191 2197689deg

934deg

1084deg 1019deg

1708 1701

2139 2139





Si1-N1 18929(19) Si1-N2 1875(2) Si2-O1 17081(17) Si2-N3 18776(19)


6941(9) N3-Si2-N4 6954(8)







- 58 -


Phosphasilene













oligomerize[126c]















- 59 -


aLSiCl



aL) 31






was easily


26[31a]





The 29





[31b] One





ppm)[31b]


- 60 -







aLSi-P




iPr2 derivative

[31b] The Si1-P1


pm) in the aLSi-P



subunit






- 61 -


10854(8)












72 yield





tBu






P-NMR spectrum



- 62 -








Phosphasilene[128]





(tBu3Si)2SiSi(Si














N2-Si1-N1 7078(11) P1-Si1-P1rsquo 10766(4)


- 63 -



















aLSiCl (1870(2) pm and 1917(2) pm)





- 64 -


















silylene 30 (0920)




- 65 -




























The


- 66 -




(Scheme 327)




















- 67 -





(Scheme 329) The



Si-N






(right)




N1 1832(7) Si1-N2 1827(7) Si1-N3 1705(7) Si2-N3 1780(7) Si3-N3



1248(4) Si2-N3-Si3 1179(4)


- 68 -















I58[61]

and

I64[65]










- 69 -












compound 35[33b]



13C-

and 29









- 70 -


singlet in the 29



tBu

iPr)

[31b]






31G(d)][101c 119]











(R = tBu

iPr)



- 71 -






by theoretical

calculation






O2-C3 13028


complex 36






36[33b]


(Scheme 333)


- 72 -













IV atom Si1 and the









complex[72b 77 135]




- 73 -


-Pd













23038(11) Si1-O1 1694(3) Si1-N1 1789(4) Si2-O2 1675(3) Si2-N5 1862(3)



Si2Si1

C1

Pd

Si3

213 pm

233 pm236 pm

230 pm

O1 O2


- 74 -

7861(11) Si2-Pd1-C1 7681(11) Si3-Pd1-C1 16783(12)


tBu groups









The 29



complexes[71 137]





The



)[135c 135f 136a]









335


- 75 -
















minus1


donor than PIII





minus1


- 76 -



and the first bis-






aLSi-Fc-Si


aLGe-Fc-Ge



PhD thesis[33a]









quantitatively














- 77 -






Si-NMR spectrum










The GeII centers






tBuC(N-Dip)2)




bidentate ligand


- 78 -




1979(9) Ge(2)-C(7) 1983(11) Ge(1)-N(1) 2027(8) Ge(1)-N(2) 2006(8)

Ge(2)-N(3) 2022(7) Ge(2)-N(4) 2037(7) C(1)-Ge(1)-N(2) 983(3) C(1)-Ge(1)-

N(1) 955(3) N(2)-Ge(1)-N(1) 653(3) C(7)-Ge(2)-N(3) 953(4) C(7)-Ge(2)-


Ge2-C8 19774(19) Ge1-N1 20261(16) Ge1-N2 20247(17) Ge2-N3

20402(15) Ge2-N4 20162(16) C1-Ge1-N1 9662(7) C1-Ge1-N2 9445(7) N1-


6459(6)




(Figure 323)


- 79 -







ferrocene molecules

6 9 0 6 9 5 7 0 0 7 0 5 7 1 0 7 1 5 7 2 0

m z

0

1 0

2 0

3 0

4 0

5 0

6 0

7 0

8 0

9 0

1 0 0

0

1 0

2 0

3 0

4 0

5 0

6 0

7 0

8 0

9 0

1 0 0

Re

lative

Abu

nda

nce

7 0 3 3 2 9

7 0 4 3 3 2

7 0 5 3 3 47 0 1 3 3 4

7 0 6 3 2 96 9 0 2 4 9 6 9 5 2 2 5 7 1 7 3 4 57 1 0 4 7 3

7 0 3 3 3 1

7 0 4 3 3 4

7 0 5 3 3 87 0 1 3 3 6

7 0 6 3 3 17 1 0 3 3 5

N L 3 1 3 E 7


N L 4 9 7 E 5


p a C hrg 1





- 80 -


recently[139]






transition-metals




0[32a


complex I65-Mo[66b]



[140] was





I

complex 41[33a]


42[33a]




- 81 -











42 δ = 699 737 and 891 ppm) In the 29













complex 41a[141]



[142] (21348(5) pm)


[143] (2228(2) pm) in


[141] (22060(6) and 22017(6) pm)






- 82 -





21252(14) Co1-Si2 21200(14) Si1-C6 1894(5) Si2-C11 1887(5) Si1-N1


9389(5) N1-Si1-N2 6847(15) N3-Si2-N4 6866(16) C6-Si1-Co1 13254(14)



- 83 -

C11 1961(4) Ge1-N1 2020(3) Ge1-N2 2031(3) Ge2-N3 2041(3) Ge2-N4

2029(3) Ge1-Co1-Ge2 9279(2) N1-Ge1-N2 6490(11) N3-Ge2-N4 6485(11)

C6-Ge1-Co1 13280(10) C11-Ge2-Co1 13140(10)



(2262(1) pm) and


4-((


and 25036(3) pm)[90d]


















- 84 -


tBu groups at δ =





of 41 In the 13






(ν = 1968 cmminus1

)[141]










tBu groups at δ =



Si-



- 85 -



C-



tBuO)SirarrFe(CO)4





)[71]
















2)-C(sp

3) coupling




- 86 -




expected[148]




Thus the catalytic


(Scheme 342)








- 87 -














- 88 -














Summary

- 89 -









in 33 yield








with KC8


in very low yield


dianion (CBD2-


core

Summary

- 90 -



and





in










Summary

- 91 -








was obtained by








in high yield










activation

Summary

- 92 -














[32a]



Summary

- 93 -







silylene 30[128]




product 31[128]










Summary

- 94 -









by 13-dilithium



as orange




SiIV




Summary

- 95 -











furnished





CoI complex 41


I complex 42

[33a]


Summary

- 96 -



are not shown












2)-C(sp

3)

cross-coupling[147]



Summary

- 97 -


probed[148-150]






- 98 -


51 General section




















dichloromethane





- 99 -









1H 400 MHz

13C


Si-NMR spectra were



The 1H and

13C








119Sn

1H external SnMe4








)












- 100 -






peak)























- 101 -










tBu [152]



9 (C5H10)C=N-Dip [111] 39 aLGeCl [41]



- 102 -











(030 g 083 mmol 33)





1H NMR (40013 MHz THF-D8 298K) δ = 108 (d

3JHH = 7 Hz 6 H




13C





378 Found C 5764 H 694 N 367




- 103 -

mmol 31)

NHN

GeN

Dip

DipDip

C41H59GeN3 MW 66657



1H NMR (40013 MHz C6D6 298K) δ = 091 (d

3JHH = 68 Hz 6 H


3JHH =





13C




C NCMe)

EI-MS mz () 6674 (03 [M]+) 4912 (100 [M -

iPr2C6H3NH]

+)


C 7354 H 868 N 613














- 104 -






C66H100Ge4K2N4O2 MW 135028


Found C 7821 H 999 N 281


C46H65Ge2N3 MW 80531








017 mmol 66)




- 105 -

1H NMR (40013 MHz C6D6 298K) δ = 107 (d

3JHH = 7 Hz 12 H


3JHH = 7




3JHH = 7 Hz 2 H



arom H)

13C






NCMe)





C 6884 H 800 N 516










- 106 -



dark red crystals



1H NMR (40013 MHz C6D6 298K) δ = 085 (d

3JHH = 7 Hz 6 H


3JHH = 7


3JHH = 7 Hz 6 H CHMe2) 129 (d




3JHH



721 (m 9 H arom H)

13C






NCMe)

119Sn NMR

(C6D6) δ = -197

UV-vis λ [nm] = 314 (15000) 363 (14500) 541 (2800)




Found C 6444 H 764 N 477


- 107 -


C37H48N2 MW 52079














1H NMR (40013 MHz CDCl3 298K) δ = 117 (d

3JHH = 7 Hz 6 H


3JHH = 7




arom H)

13C





CN) 1658 (Ph-CN)



8518 H 927 N 547


- 108 -


N

N

Ph

Dip

Dip

Cl

Ge












1H NMR (40013 MHz C6D6 298K) δ = 097 (d

3JHH = 7 Hz 3 H


3JHH = 7

Hz 3 H CHMe2) 121-127 (m 9 H CHMe2) 128-139 (m




3JHH = 7 Hz 1 H



13C





295 (Cy-CH2) 315 (Cy-CH2) 1089 (Cy-CCN) 1234-1476

(arom C) 1651 (Cy-CN) 1688 (Ph-CN)



Found C 7073 H 762 N 457


- 109 -


C37H46GeN2 MW 59142


ylidene 15[113]









1H NMR (40013 MHz C6D6 298K) δ = 115 (d

3JHH = 7 Hz 6 H


3JHH = 7




3JHH =

44 Hz 1 H C=CH) 675- 725 (m 11 H arom H)

13C




1117 (Cy-CCN) 1236-1431 (arom C) 1473 1474 (Cy-CN

Ph-CN)

IR (KBr cm-1

) 704 (s) 787 (s) 939 (m) 1104 (s) 1135 (s) 1204 (s) 1248 (s)

1296 (s) 1322 (s) 1365 (s) 1439 (s) 1461 (s) 1535 (m) 1600

(s) 2822 (m) 2865 (s) 2922 (s) 2957 (w) 3022 (w) 3061 (m)



C 7495 H 800 N 484


- 110 -


C37H49GeN3 MW 60845








1H NMR (40013 MHz C6D6 298K) δ = 106 (d

3JHH = 7 Hz 3 H



154 (s 2 H NH2) 200-213 (m 4 H Cy-CH2) 346 (sept


3JHH = 7 Hz 1 H



13C





293 (Cy-CH2) 315 (Cy-CH2) 1023 (Cy-CCN) 1234-1462

(arom C) 1643 (Cy-CN) 1669 (Ph-CN)

IR (KBr cm-1

) 561 (s) 704 (s) 752 (s) 796 (s) 839 (m) 922 (s) 1096 (s)

1143 (s) 1174 (s) 1252 (s) 1304 (s) 1360 (s) 1430 (s) 1543

(s) 2865 (m) 2961 (s) 3021 (w) 3048 (m) 3343 (w) 3430

(w)


C 7272 H 810 N 683


- 111 -










1H NMR (40013 MHz C6D6 298K) δ = 111 (d

3JHH = 7 Hz 3 H



166 (s 1 H OH) 195-221 (m 4 H Cy-CH2) 335 (sept


3JHH = 7 Hz 1 H



13C





291 (Cy-CH2) 314 (Cy-CH2) 1028 (Cy-CCN) 1233-1464

(arom C) 1647 (Cy-CN) 1666 (Ph-CN)

IR(KBr cm-1

) 561 (s) 713 (s) 743 (s) 770 (s) 791 (s) 839 (s) 926 (m)

1056 (m) 1104 (s) 1148 (s) 1170 (s) 1257 (s) 1313 (s) 1339

(s) 1365 (s) 1430 (s) 1470 (s) 1539 (s) 2861 (s) 2961 (s)

3018 (w) 3057 (m) 3643 (m)




- 112 -

Found C 7300 H 786 N 464


C28H38N2 MW 40230













1H NMR (40013 MHz CDCl3 298K) δ = 109 (d

3JHH = 7 Hz 6 H


3JHH = 7




1203 (d 3JHH = 7 Hz 1 H NH)

13C




(Cy-CCN) 1226 1228 1275 1282 1284 1371 1389

1453 (arom C) 1576 (Cy-CN) 1673 (PhCN)



- 113 -


8270 H 977 N 679













1H NMR (40013 MHz C6D6 298K) δ = 106 (d

3JHH = 7 Hz 3 H


3JHH = 7






3JHH = 7 Hz


1 H arom H) 705-724 (m 7 H arom H)

13C





- 114 -

293 (Cy-CH2) 312 (Cy-CH2) 537 (CHMe2) 1068 (Cy-

CCN) 1239 1250 1267 1271 1288 1294 1388 1410

1446 1469 (arom C) 1620 (Cy-CN) 1654 (Ph-CN)


Found C 6426 H 725 N 551










287 mmol 57 )



1H NMR (40013 MHz C6D6 298K) δ = 113 (d

3JHH = 7 Hz 6 H


3JHH = 7




3JHH =

42 Hz 1 H C=CH) 701-726 (m 8 H arom H)

13C


CH2) 247 (CHMe2) 254 (Cy-CH2) 257 (CHMe2) 286


- 115 -


1125 (Cy-CCN) 1248 1287 1296 1354 1391 1411

1421 1490 (arom C) 1682 (Cy-CN) 1709 (Ph-CN)


Found C 6203 H 517 N 679




tBu













(s 2 H SiHCl) 733- 746 (m 10 H arom H)

13C


1276 1285 1297 1337 (arom C) 1711 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = -1110

IR(KBr cm-1

) 606 (s) 658 (m) 711 (s) 733 (s) 760 (s) 789 (s) 934 (s)

1068 (s) 1200 (s) 1269 (s) 1378 (s) 1486 (s) 1550 (s) 1566

(s) 1612 (s) 1783 (w) 1826 (w) 1950 (w) 1969 (w) 2000


- 116 -

(w) 2135 (s) 2188 (s) 2909 (s) 2934 (s) 2971 (s) 3232 (m)



Found C 5971 H 797 N 913


C30H46N4OSi2 MW 53488










731(m 10 H arom H)

13C


1277 1291 1299 1349 (arom C) 1623 (NCN)

29Si

1H NMR (7949 MHz C6D6 298K) δ = -161

IR(KBr cm-1

) 608 (s) 709 (s) 746 (s) 790 (s) 892 (m) 972 (s) 1032 (m)

1070 (m) 1208 (s) 1268 (m) 1359 (s) 1412 (s) 1446 (s)

1476 (s) 1577 (m) 1648 (m) 1778 (w) 1826 (w) 1899 (w)

1970 (w) 2248 (w) 2867 (s) 2902 (s) 2928 (s) 2964 (s)

3065 (m)


- 117 -



Found C 6688 H 857 N 1046












(m 4 H CH2) 295 (m 4 H CH2) 504 (s 4 H =CH) 686-

707 (m 10 H arom H)

13C


(CMe3) 760 (=CH) 1277 1293 1296 1335 (arom C)

1690 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = 328

IR(KBr cm-1

) 607 (s) 644 (s) 698 (s) 750 (s) 792 (s) 925 (m) 1021 (m)

1075 (s) 1209 (s) 1267 (s) 1320 (m) 1361 (s) 1407 (s)

1444 (s) 1475 (s) 1578 (m) 1647 (m) 1775 (w) 1823 (w)


- 118 -

1902 (w) 1962 (w) 2280 (w) 2791 (s) 2855 (s) 2913 (s)

2975 (s) 3023 (m) 3063 (w)



Found C 6387 H 837 N 805


C21H41N2PSi3 MW 43679


(302 mg 102





085 mmol 83)



1H NMR (40013 MHz C6D6 298K) δ = 058 (d

3JP-H = 44 Hz 18 H


734-741 (m 3 H arom H)

13C

1H NMR (10061 MHz C6D6 298K) δ = 44 (d

3JC-P = 100 Hz


1292 1293 1344 (arom C) 1572 (d 3JC-P = 95 Hz

NCN)

29Si

1H NMR (7949 MHz C6D6 298K) δ = 31 (d

1JSi-P = 229 Hz


31P NMR (81012 MHz C6D6 298K) δ = - 2110


- 119 -



C30H46N4P2Si2 MW 58083





mg 025 mmol 72)




733 (m 10 H arom H)

13C


(CMe3) 1256 1276 1294 1359 (arom C) 1710 (NCN)

29Si

1H NMR (7949 MHz THF-D8 298K) δ = 267 (t

1JSi-P = 998 Hz)

31P NMR (81012 MHz THF-D8 298K) δ = - 1649


5802361


- 120 -




(336 mg 114










689 Found C 4195 H 701 N 706


C44H66N4O2Si2 MW 73919









- 121 -





174 (s 18 H ArC(CH3)3) 693 - 713 (m 8 H arom H) 754


13C


(NC(CH3)3) 350 (ArC(CH3)3) 530 (NC(CH3)3) 1096

1243 1276 1295 1297 1313 1341 1552 (arom C)

1636 (NCN)

29Si

1H NMR (7949 MHz C6D6 298K) δ = -240


Found C 7075 H 930 N 756


C88H132N8O4PdSi4 MW 158480








- 122 -






(s 9 H C(CH3)3) 114 (s 9 H C(CH3)3) 116 (s 9 H

C(CH3)3) 131 (s 9 H C(CH3)3) 139 (s 9 H C(CH3)3)155

(s 9 H C(CH3)3) 168 (s 9 H C(CH3)3) 177 (s 9 H

C(CH3)3) 180 (s 9 H C(CH3)3) 185 (s 9 H C(CH3)3) 212

(s 9 H C(CH3)3) 659 (s 1 H SiH) 686- 789 (m 22 H


13C

1H NMR (10061 MHz C6D6 298K) δ = 309 (C(CH3)3) 311

(C(CH3)3) 314 (C(CH3)3) 316 (C(CH3)3) 318 (C(CH3)3)

319 (C(CH3)3) 320 (C(CH3)3) 322 (C(CH3)3) 328

(C(CH3)3) 332 (C(CH3)3) 333 (C(CH3)3) 343 (C(CH3)3)

349 350 351 357 526 527 537 539 540 541 542

561 1112 1225 1236 1243 1256 1258 1271 1285

1287 1289 1291 1293 1294 1302 1303 1318 1323

1324 1326 1340 1342 1378 1380 1381 1409 1430

1533 1559 1585 1613 1622 1654 1731 1742

29Si


658 (LSiPd)

IR(KBr cm-1

) 623 (m) 706 (m) 764 (m) 860 (m) 1056 (m) 1108 (m) 1206

(m) 1272 (m) 1365 (m) 1418 (s) 1446 (m) 1476 (m) 1446

(m) 1476 (m) 1495 (m) 1591 (m) 2135 (w) 2875(m) 2906

(s) 2964 (s) 3061 (w)


707 Found C 6616 H 875 N 676


- 123 -















451 (t 3JHH = 15 Hz 4 H FeCH) 472 (t

3JHH = 15 Hz 4 H

FeCH) 692- 707 (m 10 H arom H)

13C



1294 1305 1349 (arom C) 1604 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = 433



Found C 6803 H 767 N 778


- 124 -















(t 3JHH = 16 Hz 4 H FeCH) 471 (t

3JHH = 16 Hz 4 H


H)

13C



1290 1302 1369 (arom C) 1659 (NCN)


C 6655 H 701 N 707


- 125 -


tBu

N

N

tBu

PhSi

tBu

N

N

tBu

Ph Si

Co

Fe













440 (t 3JHH = 16 Hz 4 H FeCH) 461 (t

3JHH = 16 Hz 4 H


692- 696 (m 6 H arom H) 720- 723 (m 2 H arom H)

13C



(SiC) 1291 1297 1300 1343 (arom C) 1673 (NCN)

29Si

1H NMR (7949 MHz CDCl3 298K) δ = 820



Found C 6612 H 724 N 686


- 126 -


tBu

N

N

tBu

PhGe

tBu

N

N

tBu

Ph Ge

Co

Fe













438 (t 3JHH = 15 Hz 4 H FeCH) 459 (t

3JHH = 15 Hz 4 H


695- 698 (m 6 H arom H) 714- 718 (m 2 H arom H)

13C



(GeC) 1287 1296 1300 1361(arom C) 1680 (NCN)


Found C 5942 H 664 N 590


- 127 -











461 (m 4 H FeCH) 476 (m 4 H FeCH) 523 (s 10 H

CoCH) 683- 695 (m 6 H arom H) 702- 706 (m 2 H

arom H) 745- 748 (m 2 H arom H)

13C



(CoCH) 1287 1296 1300 1324 (arom C) 1687 (NCN)

2078 (br CO)

29Si

1H NMR (7949 MHz C6D6 298K) δ = 857

IR(KBr cm-1

) 500 (m) 539 (w) 564 (m) 628 (s) 703 (m) 757 (s) 792 (m)

825 (w) 1028 (m) 1081 (w) 1146 (m) 1199 (s) 1275 (m)

1360 (m) 1388 (m) 1417 (s) 1438 (w) 1474 (m) 1520 (s)

1641 (s) 1888 (s) 2869 (s) 2901 (m) 2926 (m) 2965 (s)

1520 (s) 3097 (w)



- 128 -

556 Found C 6287 H 630 N 571


C48H54Fe3N4O8Si2 MW 103867










H) 736- 739 (m 2 H arom H)

13C



1287 1303 1308 (arom C) 1704 (NCN) 2169 (CO)

29Si

1H NMR (7949 MHz C6D6 298K) δ = 1050

IR(KBr cm-1

) 630 (s) 765 (w) 1028 (m) 1035 (m) 1200 (m) 1370 (w)

1400 (m) 1474 (w) 1609 (w) 1648 (w) 1900 (s) 1948 (s)

1996(w) 2026 (s) 2865 (w) 2930 (m) 2965 (m)


539 Found C 5623 H 517 N 566

References

- 129 -

6 REFERENCES



353


3877












2010 16 436


1955 77 884











Chem Int Ed 2003 42 2222




Chem Soc 1994 116 3667







References

- 130 -










5683













11366


Science 2008 321 1069




12315











9701




References

- 131 -

2008 47 1650






121 347







Int Ed 2011 50 5374


1991 1302


2004 630 2090



4130


1994 33 1156


Int Ed 1997 36 261


Inorg Chem 1997 36 5202



2008 130 12268



127 17530











References

- 132 -


















2012 51 399


5058















2011 44 588









References

- 133 -










20 1190



Allg Chem 2001 627 836




Soc 1996 118 10457





3655






Soc 2011 133 5103



Soc 1996 118 6317


Chem Rev 2005 105 3842










Phys 2000 2 2137

References

- 134 -



Phys Rev 1988 37 785









Chem Soc 2006 128 1023










2005 127 3516


2004 43 1419



2343




2003 pp 2217













References

- 135 -



CT 2004
























2868

















References

- 136 -












Chem Int Ed 2007 46 4141



2009 82 793







Chem 2011 50 8502




1804

















7162

References

- 137 -




Appendix

- 138 -

7 APPENDIX

71 Abbreviations



mmol millimole(ar)





















Et ethyl t triplet







IR infrared

K Kelvin


functions aL PhC(

tBuN)2








Appendix

- 139 -

GeN

N

GeN

Dip

Dip

DipCl

N

SnN

Dip

Dip

GeNN

SnN

Dip

DipDip

N

Dip

6 7


1 2 3 4

5 8 9

10 11 12 13 14

15 16 17 18

19 20 21 22

Appendix

- 140 -

23 24 25 26

27 28 29

30 31 32 33

34 35 36

tBu

N

N

tBu

Ph

Si

Cl

37 38 39 40

Appendix

- 141 -

tBu

N

N

tBu

PhSi

tBu

N

N

tBu

Ph Si

Co

Fe

41 42 43

44 45 46

47a 47b 48a 48b

Appendix

- 142 -



Compound 3 4 5

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C50 H88 Ge2 K2 N2 O4

100460

150(2)

71073

Triclinic

P-1

106989(7) pm

114137(7) pm

122625(8) pm

74158(6) deg

76395(6) deg

83400(5) deg

139807(16)

1

1193

1263

536

028 x 02 x 018

326 to 2500deg

-12lt=hlt=12

-13lt=klt=13

-14lt=llt=14

12268

4910 [R(int) = 00358]

996


100000 and 094847


4910 0 281

0940

R1 = 00328 wR2 = 00638

R1 = 00538 wR2 = 00666

0456 and -0223

C41 H5 Ge N3

66650

150(2)

71073

Triclinic

P-1

91129(6) pm

113531(7) pm

190282(10) pm

100360(5) deg

101854(5) deg

98627(5) deg

185918(19)

2

1191

0855

716

039 x 012 x 007

297 to 2500deg

-10lt=hlt=10

-13lt=klt=13

-22lt=llt=22

14570

6543 [R(int) = 00560]

998


0943 and 0777


6543 0 420

0785

R1 = 00399 wR2 = 00513

R1 = 00853 wR2 = 00566

0577 and -0317

C66 H102 Ge4 K2 N4 O2

135208

150(2)

71073

Monoclinic

P21n

12370(3) pm

148433(14) pm

188725(19) pm

90059(8)deg

96311(14)deg

90082(13)deg

34442(10)

2

1304

1892

1416

030 x 025 x 015

292 to 2500deg

-14lt=hlt=14

-15lt=klt=17

-14lt=llt=22

17371

6032 [R(int) = 00487]

995

Analytical

0807 and 0584


6032 2 364

0911

R1 = 00424 wR2 = 00801

R1 = 00874 wR2 = 00885

0497 and -0457

Appendix

- 143 -


Compound 6 8 12

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C46 H65 Ge2 N3

80519

150(2)

71073

Monoclinic

C2c

44536(2) pm

98204(5) pm

218135(10) pm

90deg

116030(4)deg

90deg

85727(7)

8

1248

1436

3408

038 x 024 x 010

305 to 2500deg

-49lt=hlt=52

-10lt=klt=11

-24lt=llt=25

20162

7493 [R(int) = 00954]

992


100000 and 074676


7493 0 476

0917

R1 = 00559 wR2 = 00778

R1 = 01461 wR2 = 00966

0590 and -0578

C46 H65 Ge N3 Sn

85129

150(2)

71073

Triclinic

P-1

867780(10) pm

120514(4) pm

210797(6) pm

96333(2)deg

97393(2)deg

99141(2)deg

213908(10)

2

1322

1320

888

016 x 014 x 012

295 to 2500deg

-10lt=hlt=10

-14lt=klt=14

-25lt=llt=25

16936

7496 [R(int) = 00251]

994


100000 and 099037


7496 0 495

1001

R1 = 00309 wR2 = 00706

R1 = 00437 wR2 = 00733

1468 and -0424

C37 H48 N2

52077

150(2)

71073

Triclinic

P-1

108485(5) pm

127284(7) pm

132348(4) pm

65748(4)deg

86290(3)deg

71699(5)deg

157759(12)

2

1096

0063

568

029 x 022 x 018

298 to 2500deg

-11lt=hlt=12

-15lt=klt=15

-15lt=llt=15

13428

5541 [R(int) = 00203]

998

None

09888 and 09820


5541 0 364

1029

R1 = 00439 wR2 = 00900

R1 = 00633 wR2 = 00963

0188 and -0193

Appendix

- 144 -


Compound 14 16 17

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C37 H46 Cl Ge N2

62680

150(2)

71073

Monoclinic

P21c

117621(2) pm

175495(4) pm

166051(3) pm

90deg

107053(2)deg

90deg

327691(11)

4

1270

1044

1324

040 x 032 x 022

342 to 2500deg

-13lt=hlt=13

-19lt=klt=20

-19lt=llt=18

16923

5742 [R(int) = 00250]

997


100000 and 082078


5742 0 378

1044

R1 = 00328 wR2 = 00709

R1 = 00496 wR2 = 00742

0736 and -0362

C37 H46 Ge N2

59135

150(2)

71073

Triclinic

P-1

108388(6) pm

127885(7) pm

132778(4) pm

66971(4)deg

85749(3)deg

71833(5)deg

160695(13)

2

1222

0980

628

029 x 015 x 007

307 to 2500deg

-12lt=hlt=12

-15lt=klt=15

-15lt=llt=15

13501

5636 [R(int) = 00366]

996


100000 and 092510


5636 0 369

1031

R1 = 00489 wR2 = 01180

R1 = 00691 wR2 = 01242

0539 and -0501

C37 H49 Ge N3

60838

150(2)

71073

Monoclinic

P21c

117714(4) pm

174309(6) pm

166868(6) pm

90deg

106866(4)deg

90deg

32766(2)

4

1233

0964

1296

030 x 023 x 019

342 to 2500deg

-8lt=hlt=13

-10lt=klt=20

-19lt=llt=16

12816

5749 [R(int) = 00325]

998


100000 and 095425


5749 0 378

1060

R1 = 00464 wR2 = 01084

R1 = 00699 wR2 = 01133

1717 and -0738

Appendix

- 145 -


Compound 18 20 22

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C37 H48 Ge N2 O

60936

150(2)

71073

Monoclinic

P21c

117560(3) pm

174116(5) pm

166421(4) pm

90deg

106992(3)deg

90deg

325778(15)

4

1242

0971

1296

031 x 014 x 005

343 to 2500deg

-13lt=hlt=13

-20lt=klt=20

-19lt=llt=19

23624

5720 [R(int) = 00371]

998


100000 and 083390


5720 0 379

1018

R1 = 00336 wR2 = 00752

R1 = 00516 wR2 = 00789

0521 and -0366

C28 H38 N2

40260

150(2)

71073

Monoclinic

P21c

94924(4) pm

256583(9) pm

107465(5) pm

90deg

110403(5)deg

90deg

245320(18)

4

1090

0063

880

017 x 015 x 013

343 to 2500deg

-11lt=hlt=10

-30lt=klt=27

-12lt=llt=11

8561

4313 [R(int) = 00209]

997


100000 and 099057


4313 0 281

1041

R1 = 00476 wR2 = 01015

R1 = 00771 wR2 = 01083

0253 and -0194

C28 H37 Cl Ge N2 O

52564

150(2)

71073

Triclinic

P-1

89021(3) pm

107319(4) pm

151176(6) pm

75734(4)deg

74781(3)deg

75311(3)deg

132282(8)

2

1320

1281

552

020 x 012 x 008

354 to 2500deg

-10lt=hlt=10

-12lt=klt=12

-15lt=llt=17

9246

4654 [R(int) = 00211]

997


100000 and 086160


4654 0 304

0946

R1 = 00274 wR2 = 00579

R1 = 00386 wR2 = 00597

0394 and -0264

Appendix

- 146 -


Compound 23 27 28

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C28 H36 Cl2 Ge N2

54408

150(2)

71073

Monoclinic

C2c

279616(13) pm

113538(3) pm

177729(7) pm

90deg

109718(5)deg

90deg

53115(4)

8

1361

1374

2272

021 x 017 x 015

332 to 2500deg

-25lt=hlt=33

-7lt=klt=13

-21lt=llt=20

10951

4663 [R(int) = 00459]

997


100000 and 091223


4663 0 304

0856

R1 = 00372 wR2 = 00584

R1 = 00684 wR2 = 00620

0589 and -0533


60780

150(2)

71073

Monoclinic

P21c

121593(5) pm

162045(6) pm

171248(7) pm

90deg

98177(4)deg

90deg

33399(2)

4

1209

0295

1304

030 x 015 x 005

335 to 2500deg

-14lt=hlt=13

-16lt=klt=19

-20lt=llt=20

23741

5865 [R(int) = 00491]

998


100000 and 086688


5865 172 490

1035

R1 = 00543 wR2 = 01080

R1 = 00905 wR2 = 01194

0310 and -0412

C30 H46 N4 O Si2

53489

150(2)

71073

Orthorhombic

Fdd2

31188(2) pm

39120(3) pm

102620(6) pm

90deg

90deg

90deg

125204(14)

16

1135

0141

4640

031 x 011 x 007

334 to 2500deg

-28lt=hlt=36

-46lt=klt=45

-12lt=llt=12

11517

4372 [R(int) = 00656]

997


100000 and 097469


4372 1 346

0897

R1 = 00488 wR2 = 00604

R1 = 00754 wR2 = 00650

0328 and -0229

Appendix

- 147 -


Compound 29 30 31

Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C38 H58 N4 Ni O Si2

70177

150(2)

71073

Triclinic

P-1

98776(8) pm

129530(11) pm

155488(13) pm

81634(7)deg

83316(7)deg

82826(7)deg

19430(3)

2

1200

0594

756

020 x 009 x 007

330 to 2500deg

-11lt=hlt=11

-15lt=klt=13

-18lt=llt=18

14961

6828 [R(int) = 00414]

997


100000 and 091998


6828 0 474

0948

R1 = 00386 wR2 = 00807

R1 = 00605 wR2 = 00853

0407 and -0240

C21 H41 N2 P Si3

43680

173(2)

71073

Orthorhombic

Pbca

193556(7) pm

142399(4) pm

199777(6) pm

90deg

90deg

90deg

55063(3)

8

1054

0239

1904

039 x 036 x 016

351 to 2500deg

-13lt=hlt=23

-16lt=klt=16

-23lt=llt=22

19912

4836 [R(int) = 00961]

998


09627 and 09125


4836 18 287

0906

R1 = 00571 wR2 = 00889

R1 = 01270 wR2 = 01032

0316 and -0214

C44 H60 N4 P2 Si2

76308

173(2)

71073

Monoclinic

C2c

23841(3) pm

101993(12) pm

19369(2) pm

90deg

108346(12)deg

90deg

44703(9)

4

1134

0184

1640

076 x 057 x 055

353 to 2500deg

-28lt=hlt=28

-12lt=klt=12

-20lt=llt=23

16197

3927 [R(int) = 00447]

997


09053 and 08725


3927 0 251

1034

R1 = 00618 wR2 = 01393

R1 = 00843 wR2 = 01489

0721 and -0649

Appendix

- 148 -



Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)


140312

150(2)

71073

Triclinic

P-1

105159(4) pm

127622(6) pm

269391(12) pm

90310(4)deg

90855(3)deg

102927(3)deg

35232(3)

2

1323

1000

1456

013 x 012 x 009

336 to 2500deg

-12lt=hlt=12

-15lt=klt=15

-29lt=llt=32

25757

12396 [R(int) = 00546]

997


09154 and 08810


12396 536 816

2077

R1 = 01231 wR2 = 01906

R1 = 01495 wR2 = 01944

1510 and -4753

C91 H139 N8 O4 Pd Si4

162786

150(2)

71073

Triclinic

P-1

145970(8) pm

151441(15) pm

232982(16) pm

71358(8)deg

74666(5)deg

85365(6)deg

47063(6)

2

1149

0298

1750

019 x 013 x 011

327 to 2500deg

-17lt=hlt=17

-17lt=klt=18

-27lt=llt=27

41022

16531 [R(int) = 00735]

998


09679 and 09455


16531 284 1112

0908

R1 = 00558 wR2 = 01021

R1 = 01075 wR2 = 01128

0688 and -0448

C40 H54 Fe Ge2 N4

79190

150(2)

71073

Monoclinic

P21n

10532(3) pm

20258(5) pm

18990(5) pm

90deg

10542(3)deg

90deg

39060(19)

4

1347

1927

1648

012 x 008 x 005

322 to 2500deg

-6lt=hlt=12

-22lt=klt=24

-22lt=llt=21

16887

6870 [R(int) = 01353]

997


100000 and 073478


6870 213 498

1044

R1 = 00912 wR2 = 01786

R1 = 01680 wR2 = 02282

0570 and -1404

Appendix

- 149 -



Empirical formula

Formula weight

Temperature (K)

Wavelength (pm)

Crystal system

Space group


a (pm)

b (pm)

c (pm)

α (deg)

β (deg)

γ (deg)

Volume (nm3)

Z



)

F(000)

Crystal size (mm3)


Index ranges






Refinement method






)

C40 H54 Fe Ge2 N4

79190

150(2)

71073

Monoclinic

P21n

165582(11) pm

127695(7) pm

198175(12) pm

90deg

107428(7)deg

90deg

39979(4)

4

1316

1883

1648

012 x 011 x 009

337 to 2499deg

-16lt=hlt=19

-15lt=klt=15

-23lt=llt=23

29049

7015 [R(int) = 00329]

998


100000 and 052405


7015 0 436

1065

R1 = 00263 wR2 = 00574

R1 = 00318 wR2 = 00595

0357 and -0360


82692

150(2)

71073

Monoclinic

P21c

119176(7) pm

160794(9) pm

220424(13) pm

90deg

94402(5)deg

90deg

42115(4)

4

1304

0831

1752

015 x 013 x 007

323 to 2500deg

-14lt=hlt=14

-19lt=klt=17

-16lt=llt=26

17786

7404 [R(int) = 01111]

998


100000 and 075122


7404 0 490

1052

R1 = 00717 wR2 = 01045

R1 = 01208 wR2 = 01181

0467 and -0370


91592

150(2)

71073

Monoclinic

P21c

121662(3) pm

160596(3) pm

220073(5) pm

90deg

93549(2)deg

90deg

429163(16)

4

1418

2134

1896

015 x 011 x 008

336 to 2500deg

-14lt=hlt=14

-19lt=klt=19

-26lt=llt=26

33743

7539 [R(int) = 00521]

998


100000 and 068509


7539 0 521

1259

R1 = 00400 wR2 = 00965

R1 = 00536 wR2 = 01000

0376 and -0373

Appendix

- 150 -


following tables



2times10

3)


x y z U(eq)

N(1) 1159(1) 1176(1) 6836(1) 20(1)

C(1) 1706(2) 1650(1) 6995(1) 21(1)

N(2) -1293(2) 1547(1) 7057(1) 23(1)

C(2) 789(2) 2089(1) 7078(1) 20(1)

C(3) -626(2) 2021(1) 7158(1) 20(1)

C(4) 3331(2) 1741(1) 7112(2) 29(1)

C(5) 3920(2) 2283(1) 7590(2) 34(1)

C(6) 2795(2) 2681(1) 6772(2) 35(1)

C(7) 1375(2) 2643(1) 7102(2) 27(1)

C(8) -1522(2) 2482(1) 7295(2) 21(1)

C(9) -2759(2) 2643(1) 6227(2) 27(1)

C(10) -3571(2) 3077(1) 6331(2) 33(1)

C(11) -3169(2) 3358(1) 7498(2) 35(1)

C(12) -1948(2) 3199(1) 8573(2) 32(1)

C(13) -1133(2) 2765(1) 8467(2) 27(1)

C(14) -2537(2) 1417(1) 7503(2) 35(1)

C(15) -3250(3) 920(1) 6823(2) 61(1)

C(16) -1974(3) 1344(1) 9002(2) 65(1)

C(17) 2080(2) 741(1) 6834(2) 20(1)

C(18) 2353(2) 597(1) 5670(2) 23(1)

C(19) 3237(2) 160(1) 5724(2) 29(1)

C(20) 3821(2) -131(1) 6867(2) 32(1)

C(21) 3480(2) -1(1) 7977(2) 29(1)

C(22) 2598(2) 427(1) 7984(2) 23(1)

C(23) 2150(2) 562(1) 9174(2) 28(1)

C(24) 2101(2) 91(1) 10028(2) 39(1)

C(25) 3156(2) 987(1) 10029(2) 42(1)

C(26) 1602(2) 885(1) 4374(2) 29(1)

C(27) 2645(3) 974(1) 3586(2) 53(1)

C(28) 195(3) 588(1) 3539(2) 54(1)

Appendix

- 151 -


2times10

3)


x y z U(eq)

Ge(1) 4751(1) 5279(1) 3913(1) 24(1)

Cl(1) 4863(1) 7474(1) 3443(1) 35(1)

O(1) 2591(1) 5468(1) 4187(1) 20(1)

N(1) 4469(2) 5098(1) 2623(1) 17(1)

C(1) 3006(2) 5278(2) 2582(1) 16(1)

N(2) 1482(2) 7765(2) 2375(1) 20(1)

C(2) 2432(2) 5062(2) 1801(1) 21(1)

C(3) 1144(2) 4228(2) 2174(2) 31(1)

C(4) -158(2) 4793(2) 2933(2) 30(1)

C(5) 534(2) 4844(2) 3741(1) 21(1)

C(6) 1810(2) 5684(2) 3440(1) 17(1)

C(7) 1063(2) 7152(2) 3205(1) 18(1)

C(8) 820(2) 9172(2) 2096(1) 26(1)

C(9) 397(3) 9344(2) 1159(2) 40(1)

C(10) 2058(3) 9950(2) 2035(2) 43(1)

C(11) -95(2) 7719(2) 3998(1) 18(1)

C(12) 434(2) 8108(2) 4652(1) 22(1)

C(13) -648(2) 8637(2) 5376(1) 27(1)

C(14) -2259(2) 8769(2) 5459(2) 30(1)

C(15) -2795(2) 8370(2) 4815(2) 30(1)

C(16) -1724(2) 7845(2) 4085(1) 24(1)

C(17) 5786(2) 4690(2) 1889(1) 19(1)

C(18) 6546(2) 3361(2) 1997(1) 22(1)

C(19) 7868(2) 3005(2) 1310(2) 28(1)

C(20) 8423(2) 3902(2) 552(2) 29(1)

C(21) 7656(2) 5209(2) 464(1) 26(1)

C(22) 6329(2) 5635(2) 1128(1) 21(1)

C(23) 5549(2) 7085(2) 991(2) 26(1)

C(24) 6701(3) 7932(2) 989(2) 41(1)

C(25) 4931(3) 7520(2) 84(2) 40(1)

C(26) 6001(2) 2315(2) 2820(2) 27(1)

C(27) 5775(3) 1139(2) 2495(2) 40(1)

C(28) 7175(3) 1863(2) 3471(2) 38(1)

Appendix

- 152 -


2times10

3)


x y z U(eq)

Ge(1) 967(1) 7605(1) 1823(1) 18(1)

Cl(1) 1020(1) 9314(1) 2345(1) 29(1)

N(1) 1401(1) 6550(2) 2449(1) 19(1)

C(1) 1534(1) 5601(2) 2029(2) 16(1)

Cl(2) 198(1) 7116(1) 1640(1) 31(1)

N(2) 1101(1) 7630(2) 909(1) 15(1)

C(2) 1548(1) 5691(2) 1285(2) 15(1)

C(3) 1442(1) 6764(2) 777(2) 14(1)

C(4) 1615(1) 6867(2) 172(2) 19(1)

C(5) 1945(1) 5989(2) -42(2) 26(1)

C(6) 2098(1) 4966(2) 547(2) 22(1)

C(7) 1669(1) 4652(2) 844(2) 21(1)

C(8) 1625(1) 4444(2) 2470(2) 17(1)

C(9) 1229(1) 3875(2) 2611(2) 23(1)

C(10) 1291(1) 2785(2) 2983(2) 29(1)

C(11) 1764(2) 2263(3) 3232(2) 32(1)

C(12) 2169(1) 2832(3) 3121(2) 30(1)

C(13) 2101(1) 3920(2) 2737(2) 22(1)

C(14) 1621(1) 6630(2) 3327(2) 20(1)

C(15) 1219(1) 6848(3) 3699(2) 32(1)

C(16) 2052(1) 7524(2) 3583(2) 34(1)

C(17) 833(1) 8395(2) 248(2) 17(1)

C(18) 1019(1) 9542(2) 207(2) 19(1)

C(19) 745(1) 10248(3) -431(2) 29(1)

C(20) 315(1) 9844(3) -1011(2) 36(1)

C(21) 147(1) 8718(3) -973(2) 33(1)

C(22) 399(1) 7960(2) -350(2) 20(1)

C(23) 215(1) 6700(2) -377(2) 23(1)

C(24) 329(1) 6020(3) -1045(2) 34(1)

C(25) -341(1) 6612(3) -475(2) 31(1)

C(26) 1517(1) 10001(2) 789(2) 22(1)

C(27) 1914(1) 10083(3) 375(2) 32(1)

C(28) 1463(1) 11198(2) 1144(2) 36(1)

Appendix

- 153 -


2times10

3)


x y z U(eq)

Sn(1) 4689(1) 4918(1) 3222(1) 24(1)

Sn(2) 5822(1) 5994(1) 1674(1) 30(1)

Cl(1) 4488(3) 6215(2) 3883(1) 38(1)

Cl(2) 3266(2) 3378(2) 3638(1) 39(1)

Cl(3) 7188(2) 7769(2) 1449(1) 43(1)

Cl(4) 6104(3) 5090(3) 888(1) 57(1)

Si(1) 6825(2) 4259(2) 3587(1) 17(1)

Si(2) 8610(3) 6420(2) 3531(1) 28(1)

Si(3) 9814(2) 4466(2) 3664(1) 26(1)

Si(4) 3648(2) 6680(2) 1375(1) 21(1)

Si(5) 1981(3) 4463(2) 1299(1) 30(1)

Si(6) 649(3) 6348(2) 1247(1) 30(1)

N(1) 6586(7) 2924(5) 3299(3) 20(2)

N(2) 6484(6) 3264(5) 4080(3) 16(2)

N(3) 8389(7) 5001(5) 3582(3) 23(2)

N(4) 3751(7) 7937(6) 1722(3) 22(2)

N(5) 3959(8) 7800(6) 936(3) 27(2)

N(6) 2102(7) 5865(6) 1329(3) 24(2)

C(1) 6258(8) 2470(7) 3742(4) 24(2)

C(2) 5630(8) 1296(7) 3832(3) 20(2)

C(3) 4328(9) 879(7) 3742(4) 30(2)

C(4) 3826(11) -209(8) 3826(4) 44(3)

C(5) 4613(12) -855(8) 3977(4) 47(3)

C(6) 5921(13) -450(9) 4064(4) 54(3)

C(7) 6446(10) 640(8) 3992(4) 36(3)

C(8) 6469(9) 2487(7) 2787(3) 22(2)

C(9) 7183(11) 3385(8) 2465(4) 43(3)

C(10) 5041(10) 2180(9) 2612(4) 44(3)

C(11) 7093(12) 1524(8) 2741(4) 49(3)

C(12) 6251(9) 3286(8) 4625(3) 26(2)

C(13) 4851(10) 2720(9) 4759(4) 48(3)

C(14) 7218(10) 2783(8) 4908(4) 39(3)

C(15) 6455(10) 4474(7) 4759(4) 31(2)

C(16) 7585(10) 6750(8) 3014(4) 43(3)

C(17) 8192(11) 7005(8) 4123(4) 44(3)

C(18) 10317(10) 7108(8) 3367(5) 55(4)

C(19) 10809(9) 4684(9) 3087(4) 39(3)

C(20) 9461(9) 3008(7) 3775(4) 30(2)

Appendix

- 154 -

C(21) 10726(10) 5062(9) 4232(4) 41(3)

C(22) 4144(9) 8514(7) 1315(3) 22(2)

C(23) 4603(10) 9700(7) 1286(3) 30(2)

C(24) 5918(10) 10173(8) 1332(4) 36(3)

C(25) 6315(12) 11289(9) 1292(4) 46(3)

C(26) 5453(14) 11926(9) 1203(4) 50(3)

C(27) 4158(14) 11457(9) 1158(4) 52(3)

C(28) 3726(12) 10336(8) 1194(4) 41(3)

C(29) 3829(9) 8261(7) 2260(3) 24(2)

C(30) 3041(13) 9101(10) 2358(4) 65(4)

C(31) 3223(10) 7251(8) 2537(4) 41(3)

C(32) 5223(10) 8649(10) 2438(4) 59(4)

C(33) 4252(10) 7910(8) 398(3) 30(2)

C(34) 3489(13) 8669(11) 158(4) 67(4)

C(35) 3812(13) 6813(9) 170(4) 60(4)

C(36) 5705(11) 8321(11) 315(4) 63(4)

C(37) 3040(11) 4003(8) 1778(4) 49(3)

C(38) 2431(11) 4059(8) 669(4) 44(3)

C(39) 310(10) 3713(8) 1447(5) 48(3)

C(40) -433(9) 5964(9) 1795(4) 43(3)

C(41) 921(10) 7835(9) 1209(4) 48(3)

C(42) -186(11) 5795(10) 650(4) 57(4)

C(43) -180(17) 209(14) 3445(7) 59(3)

C(44) -1099(17) -417(14) 3132(7) 58(3)

C(45) -949(16) -322(14) 2634(7) 58(2)

C(46) 75(15) 387(13) 2440(7) 58(2)

C(47) 979(17) 1008(14) 2750(6) 60(2)

C(48) 829(17) 908(15) 3251(7) 60(3)

C(49) 210(20) 473(17) 1887(7) 58(3)

C(43A) 798(17) 917(14) 2044(7) 58(3)

C(44A) 1381(17) 1418(14) 2465(7) 59(3)

C(45A) 931(16) 1088(14) 2929(7) 59(3)

C(46A) -134(15) 231(13) 2969(7) 58(2)

C(47A) -748(17) -263(14) 2547(6) 58(2)

C(48A) -289(17) 75(14) 2084(7) 58(2)

C(49A) -640(20) -111(17) 3469(8) 60(3)

C(50) 120(20) -463(18) -179(10) 106(6)

C(51) -640(30) -620(20) 236(10) 106(6)

C(52) -730(20) 250(20) 530(10) 107(6)

C(53) -70(30) 1260(20) 404(11) 109(6)

C(54) 680(20) 1409(19) -10(11) 107(6)

C(55) 780(30) 558(19) -303(11) 106(6)

C(56) 250(30) -1390(20) -499(12) 120(7)

Appendix

- 155 -

C(57) 575(16) 499(14) 4873(6) 52(3)

C(58) 807(18) -512(14) 4941(8) 53(3)

C(59) -138(17) -1326(14) 5128(7) 55(3)

C(60) -1333(18) -1140(15) 5253(8) 57(3)

C(61) -1572(16) -130(15) 5187(7) 56(3)

C(62) -620(17) 686(15) 5000(8) 53(3)

C(63) 1600(20) 1369(17) 4669(9) 59(5)

Appendix

- 156 -









palladium





Chem Eur J 2011 17 4890-4895



Matthias Driess















Appendix

- 157 -

75 Curriculum Vitae

Personal Data



Nationality Chinese

Education




Bachelor Chemistry










appropriately cited

Wenyuan Wang

Berlin Juli 2012

Synthesis and Characterization of New Low-Valent Silicon, … · 2017. 10. 26. · Synthesis and...

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Transcript of Synthesis and Characterization of New Low-Valent Silicon, … · 2017. 10. 26. · Synthesis and...