Post on 22-Jun-2020
Abnormal N-Heterocyclic Carbene Main Group Organometallic Chemistry: A Debut to the Homogeneous Catalysis
Tamal K. Sen, Samaresh Chandra Sau, Arup Mukherjee, Pradip Kumar Hota, Swadhin K.
Mandal,* Bholanath Maity, and Debasis Koley
Department of Chemical Sciences, Indian Institute of Science Education and Research-
Kolkata, Mohanpur -741252, India
*Email: sawdhin.mandal@iiserkol.ac.in
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Single-crystal structural analysis.
Shock cooled crystals were selected and mounted under nitrogen atmosphere using the X-
TEMP2.1 The data of aNHC organozinc (1) and aNHC organoaluminum (2) complexes were
measured on a Bruker TXS-Mo rotating anode with Helios mirror optics and APEX II
detector with D8 goniometer. Diffractometers were equipped with a low-temperature device
and used MoK radiation, = 71.073 pm. The data of 1 and 2 were integrated with Saint.2
The structures were solved by direct methods (Shelxs-97) and refined by full-matrix least-
squares methods against F2 (Shelxl-97).3 All non-hydrogen-atoms were refined with
anisotropic displacement parameters. The hydrogen atoms were refined isotropically on
calculated positions using a riding model. Crystallographic data (excluding structure factors)
for the structures reported in this paper have been deposited with the Cambridge
Crystallographic Data Centre. The CCDC numbers, crystal data and experimental details for
the X-ray measurements are listed in Table S1. Copies of the data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Table S1. Crystallographic and data collection parameters for adducts 1 and 2.
1 2 Empirical formula C47H67N3Si2Zn C42H53AlN2 Ccdc no. 919364 919365 Formula weight 795.61 612.84 Temperature (K) 100(2)K 100(2)K Wavelength (A° ) 0.71073 0.71073 Crystal system Monoclinic Triclinic Space group P21/n P-1 Unit cell dimensions a ( Å) 12.6449(13) 9.871(2) b (Å ) 22.610(2) 10.967(2) c (Å ) 15.8432(15) 18.786(4) α (°) 90 77.611(4) β (°) 96.468(2) 76.658(4) γ(°) 90 75.050(4) Volume (Å3) 4500.7(7) 1885.6(7) Z 4 2
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Calculated density (Mg/m3) 1.174 1.079 Absorption coefficient (mm-1) 0.633 0.083 F(000) 1712 664 Crystal size (mm) 0.2 X 0.15 X0.10 0.15 X 0.12 X 0.07 Theta range for data collection(°)
1.58-27.00 1.13- 25.06
Index ranges -16 ≤ h ≤ 16, -25 ≤ k ≤ 28, -18 ≤ l ≤ 20
-11 ≤ h ≤ 11, -13 ≤ k ≤ 13, -22 ≤ l ≤ 22
Reflections collected/unique[R(int)]
41248/9831/0.0566 25271/6652/0.0517
Completeness to 2θ = 25.00 100% 99.5% Absorption correction 'multi-scan' 'multi-scan' Maximum and minimum transmission
0.939 and 0.892 0.994 and 0.988
Refinement method Full matrix least square on F2
Full matrix least square on F2
Data/restraints/parameters 9831/0/493 6652/0/ 417 Goodness-of-fit on F2 1.014 1.020 Final R indices [I > 2σ(I)] R1 = 0.0373, wR2 = 0.0818 R1 = 0.0411, wR2 = 0.0884 R indices (all data) R1 = 0.0601, wR2 = 0.0917 R1 = 0.0690, wR2 = 0.1059 Largest difference peak andhole (e Å-3 )
0.481 and -0.293 0.205 and -0.227
General procedure for the ring-opening polymerization (ROP) of cyclic esters. In a
single necked tube fitted with standard ground joint, a toluene solution of catalyst and BnOH
were loaded inside the glovebox at room temperature. The solution was stirred for 5 min, and
then cyclic ester (required amount) was added to the solution and the tube was closed with a
glass stopper. The reaction mixture was stirred at appropriate temperature. The
polymerization mixture was quenched by addition of water (0.2 mL) and diluted with
dichloromethane. The resultant solution was poured into rapidly stirred methanol (400 mL)
solution. The ring-opened polymer was collected as the methanol insoluble white precipitates
by filtration and was dried under reduced pressure.
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Table S2. Polymerization of ε-caprolactone and -valerolactone with catalyst 1.a
Entry Monomer [M]
[M]:[Cat.]: [ROH]
(%)b conv.
Time (min.)
Mn (NMR)c
Mn (GPC)d
PDIe
1 Cl 200:1:0 65 10 - 20261 2.08 2 Cl 200:1:1 75 15 15384 24381 1.25 3 Cl 200:1:2 90 15 10097 15156 1.19
4 Cl 100:1:2 100 15 6036 9257 1.22 5 Clf 50:1:1 94 60 - 6000 1.354 6 VL 100:1:0 95 15 6394 20508 1.42 7 VL 200:1:0 95 15 11674 34984 1.44 8 VL 200:1:1 97 15 14990 28757 1.45 9 VL 300:1:1 98 15 20337 31686 1.4
aTypical polymerization reaction: To a solution of 1 (0.0097 mmol, 7.71 mg in 2.0 mL toluene) required amount of BnOH was added and stirred for further 5 min at room temperature. To the resultant mixture, cyclic ester (measured amount) was added and stirred at room temperature for a given time at 25 °C. The reaction was terminated by addition of 4 drops of water and exposure to air. bDetermined by 1H NMR spectroscopy, cDetermined by 1H NMR spectroscopy, d,e Calculated from GPC measurement.f In CH2Cl2, at room temperature using AlMe3 as catalyst.
Kinetics of ε-caprolactone and rac lactide polymerization using catalyst 1
The polymerization was performed inside a nitrogen filled glovebox using toluene as solvent.
In a single necked tube fitted with standard ground joint, a toluene solution of 1 (0.0097
mmol, 7.71 mg in 1.0 mL toluene) and BnOH (0.0194 mmol, 2.1 mg) were loaded inside the
N2 filled glovebox at room temperature. The solution was stirred for 5 min, and then cyclic
ester monomer (required amount) in 4 mL toluene was added to the solution and the tube was
closed with a glass stopper. The reaction mixture was stirred at 25 °C. Kinetic experiments
were performed by taking a small amount of aliquots (150 μL) from the reaction mixture after
O
O
aa = 1, 2
nCatalyst
O
O
na = 1, 2
a
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a certain time interval and quenched by the addition of water (100 μL). Subsequently, the
reaction mixture was dried and checked by 1H NMR spectroscopy and GPC analysis. The
conversions at different time interval were determined from the 1H NMR spectroscopy. The
relative molecular weight with respect to polystyrene standard and the poly dispersity index
(PDI) values were determined from the GPC measurements. The molecular weights of the
ring-opened polymers can be controlled as a function of the monomer to-initiator ratio (M/I)
with consistently narrow polydispersities (PDIs).
5 10 15 20 25 30 35
1.6
2.0
2.4
2.8
3.2
ln(C
L0/
CL t)
Time(min)
0 30 60 90 120 1500.5
1.0
1.5
2.0
2.5
ln(L
A0/L
At)
Time (min)
30 60 90 120
8000
12000
16000
20000
Mn(G
PC
)
[M]/[BnOH]
(a) (b)
(c)
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Fig. S1 (a) Polymerization of ε-caprolactone using aNHC based organozinc adduct 1 as
catalyst under [ε-CL]0/[catalyst]/[BnOH] = 150:1:2 ratio in 5 mL toluene at 25 °C:
logarithmic plot of ε-caprolactone consumption as a function of time showing a linear
increase. (b) Polymerization of rac-LA using aNHC based organozinc adduct 1 under [rac-
LA]0/[catalyst]/[BnOH] = 150:1:2 ratio in 5 mL toluene at 25 °C: logarithmic plot of rac-LA
consumption as a function of time showing a linear increase. (c) Polymerization of rac-LA
using aNHC based organozinc adduct 1 under [catalyst]/[BnOH] = 1:2 ratio in 5 mL toluene
at 25 °C. The controlled nature of the polymerization using the catalyst 1 is revealed in the
plots of molecular weight [Mn (GPC)] vs. monomer to benzyl alcohol ratio which shows the
gradual increase of molecular weight in a linear fashion with monomer to benzyl alcohol.
The plot of molecular weight [Mn (GPC)] vs. monomer to benzyl alcohol ratio shows the
gradual increase of molecular weight in a linear fashion with progress of the polymerization
(Fig. S1). This result indicates the controlled nature of polymerization. Also the PDI values
remain almost constant during the course of polymerization further supporting the controlled
nature of polymerization process (Fig. S1).
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Homonuclear decoupled 1H NMR spectra
We performed homonuclear decoupled 1H NMR spectrum in order to shed light into the
microstructures of the obtained polylactide (PLA). The homonuclear decoupled 1H NMR
spectrum reveals a small dependence of the PLA microstructure on the catalyst (Fig. S2).
Catalyst 1 was found more selective towards synthesis of isotactic polylactide in comparison
to catalyst 2.
Fig. S2 Homonuclear decoupled 1H NMR spectra (CDCl3, 25 °C) of the methine range of
poly-(rac)lactide obtained from rac-LA using (a) catalyst 1 and (b) catalyst 2
(a) (b)
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Fig. S3 1H NMR spectrum of recation mixture revealing the formation of intermediate compound 1I recorded in C6D6 immediately after the reaction..
NN
Zn
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Fig. S4 1H NMR spectrum of compound 1 recorded in C6D6.
NN
Zn
NMe3Si
SiMe3
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Fig. S5 13C NMR spectrum of compound 1 recorded in C6D6.
NN
Zn
NMe3Si
SiMe3
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Fig. S6 1H NMR spectrum of compound 2 recorded in C6D6.
NN
Al
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Fig. S7 13C NMR spectrum of compound 2 recorded in C6D6.
NN
Al
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Reaction of complex 1 with benzyl alcohol
Fig. S8 Stack plot of 1H NMR of compound 1 and 1with 2 equivalent of benzyl alcohol
recorded in C6D6. The resonance at 4.3 ppm corresponds to the benzyl alkoxide proton.
NN
Zn
NMe3Si
SiMe3
NN
Zn
NMe3Si
SiMe3
+ 2BnOH
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Polymerization of rac lactide without benzyl alcohol
Fig. S9 1H NMR spectrum of pure poly lactide obtained by the reaction of 1 with rac-lactide recorded in CDCl3 revealing the presence of –NSi(Me3)2 end group.
NN
Zn
NMe3Si
SiMe3
O
O
O
O
OO
N
O
O
Hn
n
SiMe3
SiMe3
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Polymerization of rac lactide in presence of benzyl alcohol
Fig. S10 1H NMR spectrum of pure poly lactide obtained by the reaction of 1and 2 equivalent of benzyl alcohol with rac-lactide recorded in CDCl3 revealing the presence of benzyloxy end group.
NN
Zn
NMe3Si
SiMe3
O
O
O
O
OO
O
O
Hn
nOHO
ab
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Thermal stability of complex 1 in tol-d8
Fig. S11 Stack plot of 1H NMR of compound 1 in tol-d8 at different temperature (25°C to 75°C) indicating the thermal stability of complex 1.
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Thermal stability of complex 2 in tol-d8
Fig. S12 Stack plot of 1H NMR of compound 2 in tol-d8 at different temperature (20°C to 140°C) indicating the thermal stability of complex 2.
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3750 3000 2250 1500
75
80
85
90
95
100%
(T
ran
mit
ten
ce)
Frequency (cm-1)
1455 cm-1
Fig.S13 IR spectra of the polylactide obtained by the reaction of rac- Lactide (100 equivqalent) and catalyst 1 (1 equivalent)
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Computational Details
All calculations were performed with Gaussian09 Quantum code.5 Geometries are optimised
using ONIOM (MO:MO)6 method implemented in Gaussian09 program package. As a higher
level we have specified whole molecule except four phenyl fragments connecting to the
imidazole ring. This higher level was treated using BP86 functional6 with triple-zeta quality
basis sets (TZVP).8 Low level of the ONIOM was treated with HF/STO-3G level of theory.9
Geometries were optimized without any symmetry constraints. Harmonic force constants
were computed at the optimized geometries to characterize the stationary points as minima or
saddle points. Single point calculations were performed of the optimized geometries using
BP86 functional incorporating higher basis sets (TZVP) for all atoms. NBO analysis10 was
performed to understand the nature of bonding in aNHC – Zn and aNHC – Al bonds. For
NBO study we have done a single-point calculation of the optimized structures of 1 and 2
with replacing the phenyl substituents with methyl groups. The charge distribution around the
carbene center was analyzed using Weinhold’s NPA (Natural Population Analysis) approach.
Wiberg bond indices were also calculated to quantify covalent interactions.11 We have
applied Bader’s AIM (Atoms-in-molecule)12 concept to characterize the electron distribution
in the aNHC – Zn and aNHC – Al complexes. Any bonded pair of atoms has a bond path, i.e.
a connecting line with maximum electron density. The bond critical (BCP) is a point on this
line where the gradient of the density is equal to zero. The magnitude of the electron density
() and its Laplacian (2) at the BCP provide information about the strength and type of
bond. The Laplacian indicates whether the density is locally concentrated (2<0) or
depleted ((2>0). Natural bond orbitals are plotted in the Chemcraft visualization
software.13
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Table S3. Cartesian coordinates (Å) of the DFT optimized structures.
1 120 X Y Z Zn -2.26821 0.97293 -0.28460 Si -3.83971 -0.99720 1.78446 Si -4.94075 -0.45456 -1.03550 N -3.64493 -0.40522 0.14995 N 0.88323 1.13040 0.00847 C 0.25900 2.75611 2.41958 H 0.45685 1.68800 2.35919 N 1.72880 -0.89123 0.01579 C -2.75415 2.79994 -1.04238 H -1.87301 3.34935 -1.41159 H -3.35158 2.58191 -1.94664 C -3.57077 3.73199 -0.12489 H -4.44526 3.22591 0.31313 H -3.95101 4.62280 -0.65973 H -2.96986 4.10827 0.71790 C -5.16974 -0.02593 2.76672 H -4.94015 1.05113 2.78844 H -5.24006 -0.38097 3.80841 H -6.16633 -0.14027 2.31091 C -4.32651 -2.84328 1.93328 H -5.34051 -3.04889 1.56230 H -4.29303 -3.14564 2.99329 H -3.62875 -3.48640 1.37624 C -2.22758 -0.85341 2.80548 H -1.43807 -1.50626 2.40613 H -2.43359 -1.17103 3.84072 H -1.82961 0.16928 2.84923 C -6.16566 1.01096 -0.92582 H -6.60274 1.08967 0.08179 H -6.99356 0.88265 -1.64301 H -5.67156 1.96781 -1.14894 C -6.02984 -2.02576 -0.94614 H -5.43335 -2.94956 -0.97560 H -6.71593 -2.03621 -1.80933 H -6.64856 -2.04989 -0.03597 C -4.23096 -0.42278 -2.81507 H -3.52459 0.40884 -2.96743 H -5.04744 -0.29387 -3.54457 H -3.71104 -1.36099 -3.06276 C -0.23510 0.27647 -0.04790 C 0.77383 2.58833 -0.11653 C 0.96005 3.16369 -1.38249 C 0.83245 4.54449 -1.49691
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H 0.96595 5.01375 -2.46137 C 0.52916 5.32402 -0.39640 H 0.43007 6.39704 -0.50546 C 0.35041 4.73831 0.84397 H 0.11276 5.36090 1.69489 C 0.46861 3.36299 1.01538 C -1.20582 2.94163 2.88445 H -1.45266 3.99470 2.97110 H -1.34644 2.47738 3.85559 H -1.88102 2.47662 2.17043 C 1.22011 3.36234 3.47443 H 1.03701 4.42369 3.60497 H 2.26095 3.22914 3.20024 H 1.06020 2.87428 4.43105 C 1.28657 2.32480 -2.63494 H 1.43879 1.29455 -2.32613 C 0.10636 2.33140 -3.63752 H -0.78329 1.91233 -3.17678 H 0.35894 1.73245 -4.50743 H -0.11689 3.33995 -3.97039 C 2.59296 2.80438 -3.31540 H 2.48234 3.80603 -3.71709 H 2.84654 2.13903 -4.13524 H 3.41872 2.80813 -2.61043 C 2.06203 0.43715 0.03446 C 3.44324 1.01171 0.02391 C 3.73599 2.17412 0.73921 H 2.96512 2.65638 1.31801 C 5.01005 2.71491 0.72120 H 5.21570 3.61520 1.28602 C 6.01696 2.10623 -0.01249 H 7.01365 2.52992 -0.02685 C 5.73908 0.95146 -0.72861 H 6.51640 0.47027 -1.30825 C 4.46603 0.40896 -0.71197 H 4.26778 -0.48562 -1.28040 C 2.68326 -2.00307 0.08611 C 3.31855 -2.27727 1.30855 C 3.04887 -1.47219 2.59732 H 2.31438 -0.70268 2.37407 C 2.45723 -2.36558 3.71633 H 1.52451 -2.82115 3.40104 H 2.25805 -1.76250 4.59698 H 3.14885 -3.15421 3.99418 C 4.33609 -0.77223 3.10167 H 4.10245 -0.14375 3.95569 H 4.77133 -0.14954 2.32734 H 5.07801 -1.50105 3.41110 C 4.22889 -3.32844 1.34595 H 4.73367 -3.56079 2.27304
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C 4.49701 -4.08217 0.21850 H 5.21052 -4.89549 0.26933 C 3.85266 -3.80337 -0.97276 H 4.06800 -4.40326 -1.84566 C 2.93157 -2.76527 -1.06832 C 2.22994 -2.50657 -2.41931 H 1.50414 -1.70921 -2.28049 C 1.46597 -3.76649 -2.89887 H 2.15543 -4.56187 -3.16219 H 0.87710 -3.52391 -3.77807 H 0.79637 -4.13240 -2.12860 C 3.22732 -2.05400 -3.51613 H 3.70725 -1.11660 -3.25676 H 2.69642 -1.91070 -4.45232 H 3.99819 -2.80123 -3.67509 C 0.30740 -0.99806 -0.03528 C -0.39467 -2.31862 -0.15017 C -0.06438 -3.41890 0.64238 H 0.71130 -3.33375 1.38790 C -0.72323 -4.62782 0.48988 H -0.45196 -5.46794 1.11622 C -1.72729 -4.76160 -0.45532 H -2.24179 -5.70650 -0.57408 C -2.07138 -3.67392 -1.24531 H -2.85312 -3.76998 -1.98785 C -1.41385 -2.46573 -1.09394 H -1.68418 -1.61752 -1.70876
2 98 X Y Z Al 1.50219 3.30024 -0.05695 N 1.12505 0.13657 -0.01776 N -1.03070 -0.26178 0.01809 C 3.17076 0.95032 -3.42009 H 3.04636 1.90928 -2.92802 H 2.63274 0.97598 -4.36288 H 4.22460 0.80545 -3.63382 C 2.62059 -0.19533 -2.53589 H 1.55827 -0.01459 -2.38997 C 3.29816 -0.21459 -1.15156 C 2.57826 -0.06339 0.03935 C 0.19416 -0.86720 -0.09333 C -2.32784 -0.94931 0.00914 C -2.70455 -1.72229 1.12131 C -3.93567 -2.36838 1.07755 H -4.24811 -2.97136 1.91828 C -4.76632 -2.25320 -0.02111 H -5.72010 -2.76631 -0.03430 C -2.60759 -0.82762 -3.61840 H -1.79192 -1.53295 -3.50234 H -2.37825 -0.18700 -4.46450
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H -3.51098 -1.38319 -3.84890 C -2.79574 0.04067 -2.34823 H -1.85418 0.54629 -2.15031 C -3.87090 1.12437 -2.61445 H -4.80323 0.67531 -2.94046 H -3.52696 1.79549 -3.39543 H -4.06384 1.70888 -1.72174 C -3.16292 -0.81196 -1.11387 C -0.83145 1.13777 0.14389 C -1.96811 2.10398 0.34197 C -2.06925 3.24192 -0.45704 H -1.34552 3.41006 -1.24173 C -3.08851 4.15953 -0.25622 H -3.14771 5.03852 -0.88538 C -4.02836 3.95259 0.74098 H -4.82507 4.66884 0.89660 C -3.94041 2.82320 1.54034 H -4.66663 2.65540 2.32528 C -2.91821 1.91068 1.34433 H -2.85301 1.04316 1.98297 C 0.53076 1.41022 0.09236 C 0.73840 4.46447 1.41212 H 0.80946 4.01665 2.41873 H -0.31450 4.75897 1.26755 H 1.31860 5.40462 1.45094 C 1.08159 3.96069 -1.94573 H 0.40113 4.83057 -1.94576 H 0.64612 3.21708 -2.63678 H 2.01959 4.30610 -2.41645 C 3.52609 3.23717 0.08485 H 3.82003 4.29607 -0.05365 H 4.04361 2.68362 -0.71643 H 3.97620 2.92662 1.04074 C 0.45429 -2.32031 -0.34614 C -0.35708 -3.03654 -1.22782 H -1.18232 -2.54662 -1.72038 C -0.11091 -4.37400 -1.48609 H -0.74929 -4.91107 -2.17587 C 0.94930 -5.02055 -0.86865 H 1.14156 -6.06710 -1.07139 C 1.76234 -4.31945 0.00899 H 2.59127 -4.81539 0.49760 C 1.51907 -2.98118 0.26835 H 2.16004 -2.45184 0.95576 C 3.20096 -0.08500 1.29979 C 2.41583 0.05832 2.62211 H 1.35487 0.08511 2.38590 C 2.65488 -1.14372 3.57172 H 2.39453 -2.08539 3.10002 H 2.04191 -1.03161 4.46088
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H 3.69251 -1.19531 3.88402 C 2.76505 1.37796 3.35306 H 3.81947 1.41143 3.60735 H 2.18935 1.45094 4.27081 H 2.53307 2.23689 2.73392 C 4.57957 -0.25494 1.33450 H 5.09071 -0.26876 2.28686 C 5.31043 -0.40676 0.16828 H 6.38427 -0.53880 0.21932 C 4.67619 -0.39165 -1.05915 H 5.25873 -0.51239 -1.96169 C 2.77699 -1.55902 -3.25493 H 3.82069 -1.76889 -3.46534 H 2.23833 -1.54378 -4.19766 H 2.38215 -2.36796 -2.64866 C -1.82055 -1.89597 2.37486 H -0.92006 -1.30086 2.24591 C -1.39803 -3.37604 2.55846 H -2.26006 -3.99847 2.77490 H -0.70293 -3.46038 3.38829 H -0.91549 -3.76064 1.66689 C -2.52972 -1.39629 3.65888 H -2.81003 -0.35205 3.57582 H -1.86004 -1.50029 4.50723 H -3.42444 -1.97556 3.86140 C -4.38212 -1.48203 -1.10202 H -5.04083 -1.39828 -1.95473
aNHC 85 X Y Z N -1.19850 0.77618 -0.00340 N 0.83440 -0.01133 -0.06782 C -2.09758 1.83449 3.34598 H -1.61317 2.53448 2.64922 H -1.44165 1.70025 4.22104 H -3.03943 2.28924 3.69251 C -2.36844 0.47781 2.65878 H -1.39564 0.07390 2.33950 C -3.21677 0.69650 1.40967 C -2.63957 0.86486 0.13230 C -0.47631 -0.39501 -0.01290 C 1.95612 -0.92822 -0.07095 C 2.27385 -1.62205 -1.26300 C 3.38390 -2.48019 -1.23768 H 3.65219 -3.02983 -2.14281 C 4.15182 -2.64000 -0.08423 H 5.01319 -3.31188 -0.08941 C 2.07282 -1.28470 3.56479 H 1.21435 -1.93248 3.33320 H 1.82535 -0.71359 4.47292 H 2.92984 -1.93377 3.80361
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C 2.40364 -0.31887 2.40747 H 1.51691 0.30754 2.22907 C 3.55847 0.62108 2.81248 H 4.46910 0.05036 3.05500 H 3.27857 1.19930 3.70657 H 3.80127 1.32879 2.00830 C 2.72034 -1.06782 1.11319 C 0.88358 1.41078 -0.10627 C 2.10588 2.22151 -0.21606 C 2.02310 3.56424 0.22410 H 1.07096 3.90710 0.63247 C 3.11442 4.42487 0.12283 H 3.01991 5.45594 0.47228 C 4.32763 3.97505 -0.41627 H 5.18440 4.64832 -0.49150 C 4.42466 2.65356 -0.86086 H 5.35915 2.28869 -1.29399 C 3.32999 1.78679 -0.76812 H 3.43842 0.76700 -1.13401 C -0.41274 1.93148 -0.04422 C -1.00232 -1.76441 0.01032 C -0.39465 -2.78475 0.77504 H 0.49465 -2.56400 1.36331 C -0.91976 -4.07822 0.78819 H -0.43107 -4.84825 1.38918 C -2.06561 -4.38702 0.04708 H -2.47625 -5.39872 0.06204 C -2.67989 -3.38570 -0.71364 H -3.57134 -3.61295 -1.30220 C -2.15604 -2.09258 -0.73699 H -2.64081 -1.32883 -1.34402 C -3.40593 1.19390 -1.00835 C -2.76433 1.46100 -2.36707 H -1.75912 1.01018 -2.35514 C -3.54207 0.83564 -3.53984 H -3.71082 -0.24321 -3.39670 H -2.97834 0.96944 -4.47597 H -4.52406 1.31264 -3.68326 C -2.57248 2.97910 -2.57357 H -3.54486 3.49775 -2.57176 H -2.08134 3.17539 -3.54023 H -1.94492 3.39158 -1.76999 C -4.79419 1.31631 -0.84432 H -5.41462 1.56792 -1.70684 C -5.39414 1.12838 0.40127 H -6.47734 1.22599 0.50607 C -4.61058 0.82595 1.51479 H -5.08785 0.69920 2.48846 C -2.97898 -0.53562 3.64230 H -3.91258 -0.16234 4.09142
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H -2.27736 -0.72583 4.46913 H -3.19672 -1.49544 3.15065 C 1.48488 -1.45687 -2.56016 H 0.63525 -0.78806 -2.35750 C 0.91298 -2.80112 -3.05408 H 1.71717 -3.50161 -3.32938 H 0.29161 -2.64243 -3.94907 H 0.29084 -3.28178 -2.28582 C 2.34013 -0.79159 -3.65918 H 2.70726 0.19646 -3.34604 H 1.74241 -0.65616 -4.57398 H 3.21177 -1.41334 -3.91775 C 3.81996 -1.93872 1.07502 H 4.42874 -2.06610 1.97308
AlMe3 35 X Y Z Zn 3.86669 -1.85397 0.04792 Si 4.98147 0.38307 1.84864 Si 5.73175 0.23633 -1.22343 N 4.91808 -0.33027 0.23604 C 2.75476 -3.45059 -0.14688 H 2.19313 -3.57105 0.79482 H 2.00079 -3.23460 -0.92244 C 3.51579 -4.74575 -0.48623 H 4.06307 -4.66612 -1.43820 H 2.82900 -5.60486 -0.58005 H 4.25349 -5.00650 0.28845 C 6.60803 -0.03422 2.74835 H 6.74388 -1.12422 2.82757 H 6.61563 0.38321 3.76830 H 7.47989 0.37144 2.21308 C 4.78783 2.27718 1.80092 H 5.60853 2.75943 1.24733 H 4.79344 2.69079 2.82225 H 3.84076 2.56822 1.32156 C 3.54535 -0.33893 2.87887 H 2.56583 -0.10337 2.43304 H 3.55302 0.08065 3.89770 H 3.61835 -1.43437 2.98563 C 7.54248 0.72364 -0.89080 H 7.61719 1.56413 -0.18337 H 8.03461 1.03674 -1.82566 H 8.11193 -0.12058 -0.47317 C 4.83932 1.72778 -2.00310 H 3.79466 1.47691 -2.24520 H 5.33602 2.04561 -2.93414 H 4.82414 2.58996 -1.31929 C 5.71899 -1.18241 -2.50120 H 6.25779 -2.06847 -2.12946 H 6.21036 -0.86589 -3.43529
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H 4.69486 -1.49184 -2.77056 Zn(Et)(N(SiMe3)2) 35
X Y Z Zn 3.86669 -1.85397 0.04792 Si 4.98147 0.38307 1.84864 Si 5.73175 0.23633 -1.22343 N 4.91808 -0.33027 0.23604 C 2.75476 -3.45059 -0.14688 H 2.19313 -3.57105 0.79482 H 2.00079 -3.23460 -0.92244 C 3.51579 -4.74575 -0.48623 H 4.06307 -4.66612 -1.43820 H 2.82900 -5.60486 -0.58005 H 4.25349 -5.00650 0.28845 C 6.60803 -0.03422 2.74835 H 6.74388 -1.12422 2.82757 H 6.61563 0.38321 3.76830 H 7.47989 0.37144 2.21308 C 4.78783 2.27718 1.80092 H 5.60853 2.75943 1.24733 H 4.79344 2.69079 2.82225 H 3.84076 2.56822 1.32156 C 3.54535 -0.33893 2.87887 H 2.56583 -0.10337 2.43304 H 3.55302 0.08065 3.89770 H 3.61835 -1.43437 2.98563 C 7.54248 0.72364 -0.89080 H 7.61719 1.56413 -0.18337 H 8.03461 1.03674 -1.82566 H 8.11193 -0.12058 -0.47317 C 4.83932 1.72778 -2.00310 H 3.79466 1.47691 -2.24520 H 5.33602 2.04561 -2.93414 H 4.82414 2.58996 -1.31929 C 5.71899 -1.18241 -2.50120 H 6.25779 -2.06847 -2.12946 H 6.21036 -0.86589 -3.43529 H 4.69486 -1.49184 -2.77056
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