Chemistry of the d-Block Elements CDM/CoordinationCh… · 3 Chemistry of the d-Block Elements B....
Transcript of Chemistry of the d-Block Elements CDM/CoordinationCh… · 3 Chemistry of the d-Block Elements B....
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Chemistry of the d-Block Elements
History:
Louis Nicolas Vauquelin16. Mai 1763 – 14. Nov. 1829
Leopold Gmelin2. Aug. 1788 – 13. Apr. 1853
Chemistry of the d-Block Elements
History:
PdNH3
NH3
H3N
H3NPd
Cl
Cl
Cl
Cl
CoIII
CN
CN
NC
NC
NC
CNLouis Nicolas Vauquelin1813
Gmelin1822
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Chemistry of the d-Block Elements
History:
1844: Peyrone’s Chloride[PtCl2(NH3)2]
1844: Reiset[PtCl2(NH3)2] !
(isomers are super-important in chemistry!)
-- note! same formula! --
cis- and trans- Platinum Isomers: Serendipity in Chemistry
"Testicular cancer went from a disease that normally killed about 80% of the patients, to one which is close to 95% curable. This is probably the most exciting development in the treatment of cancers that we have had in the past 20 years. It is now the treatment of first choice in ovarian, bladder, and osteogenicsarcoma [bone] cancers as well."
—Barnett Rosenberg, who led the research group that discovered cisplatin, commenting on the impact of cisplatin in cancer chemotherapy
Cisplatin was approved by the FDA for the treatment of genitourinary tumors in 1978.
Since then, Michigan State has collected over $160 million in royalties from cisplatin and a related drug, carboplatin, which was approved by the FDA in 1989 for the treatment of ovarian cancers.
PtNH 3
NH 3
O
O
O
O
carboplatin
Prof. Barnett Rosenberg, MSU(Prof. S.J. Lippard, MIT)
Chemistry of the d-Block Elements
Newest generation:
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Chemistry of the d-Block Elements
B. Rosenberg et al. in Nature 1965, 205, 698
Stephen J. Lippard et al. in Nature (1999), 399, 708 - 712Basis for recognition of cisplatin-modified DNA by high-mobility-group proteins
SUMMARY: The anticancer activity of cis -diamminedichloroplatinum(II) (cisplatin) arises from its ability to damage DNA, with the major adducts formed being intrastrandd(GpG) and d(ApG)
Cisplatin acts by cross-linking DNA in several different ways, making it impossible for rapidly dividing cells to duplicate their DNA for mitosis. The damaged DNA sets off DNA repair mechanisms, which activate apoptosiswhen repair proves impossible. The trans-isomer does not have this pharmacological effect.
Barnett Rosenberg, MSU (1926 - )
Chemistry of the d-Block Elements
B. Rosenberg et al. in Nature 1965, 205, 698
Stephen J. Lippard et al. in Nature (1999), 399, 708 - 712Basis for recognition of cisplatin-modified DNA by high-mobility-group proteins
SUMMARY: The anticancer activity of cis -diamminedichloroplatinum(II) (cisplatin) arises from its ability to damage DNA, with the major adducts formed being intrastrandd(GpG) and d(ApG)
Cisplatin acts by crosslinking DNA in several different ways, making it impossible for rapidly dividing cells to duplicate their DNA for mitosis. The damaged DNA sets off DNA repair mechanisms, which activate apoptosiswhen repair proves impossible. The trans isomer does not have this pharmacological effect.
Stephen J. Lippard, MIT (??? - )
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Chemistry of the d-Block Elements
B. Rosenberg et al. in Nature 1965, 205, 698
Stephen J. Lippard et al. in Nature (1999), 399, 708 - 712Basis for recognition of cisplatin-modified DNA by high-mobility-group proteins
SUMMARY: The anticancer activity of cis -diamminedichloroplatinum(II) (cisplatin) arises from its ability to damage DNA, with the major adducts formed being intrastrandd(GpG) and d(ApG)
Cisplatin acts by crosslinking DNA in several different ways, making it impossible for rapidly dividing cells to duplicate their DNA for mitosis. The damaged DNA sets off DNA repair mechanisms, which activate apoptosiswhen repair proves impossible. The trans isomer does not have this pharmacological effect.
Chemistry of the d-Block Elements
Another success story at the HEART of coordination chemistry:CardioLite
"Davison realized that fundamental coordination chemistrywould shed light on the chemical characteristics of the element technetium and that these basic chemical characteristics could be translated into the rational design of new radiopharmaceuticals," Orvig notes in the article. He calls Davison
"one of the fathers of medicinal inorganic chemistry.“
Prof. Chris Orvig, University of British Columbiataken from SNM advancing molecular imaging
Alan Davison, MIT (??? - )
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Chemistry of the d-Block Elements
Another success story at the HEART of coordination chemistry:Cardiolite
Chemistry of the d-Block Elements
The d - Block Elements
http://www.chemsoc.org/viselements/pages/pertable_fla.htm
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The d - Block Elements…my personal favorites
Chemistry of the d-Block Elements
The d - Block Elements…my personal favorites
Prof. Karl WieghardtMax-Planck-Institutefor Bioinorganic ChemistryMuelheim/Germany
Chemistry of the d-Block Elements
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The Werner & Jørgensen Controversy
Chemistry of the d-Block Elements
Sophus Mads Jørgensen 1837 – 1914
Alfred Werner – Founder of Coordination Chemistry
“Dot” Representation:
Pentachlorophosphorous PCl5PCl3 • Cl2
Copper(II) Sulfate PentahydrateCuSO4 • 5H2O
Copper(II) Acetate HydrateCu(CH3COO)2 • H2O
Hex(a)ammin Cobalt(III) ChlorideCoCl3 • 6NH3
Chemistry of the d-Block Elements
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Alfred Werner
Chemistry of the d-Block Elements
Seite 111 des 17-jährigen(!) Alfred Werner‘s „Einleitung in die Chemie“ (1883 – 1884) über die Formulierung des PCl5 als molecular compound PCl3 • Cl2
Alfred Werner – Founder of Coordination Chemistry
Copper(II) Acetate HydrateCu(CH3COO)2 • H2O
Hex(a)ammin Cobalt(III) ChlorideCoCl3 • 6NH3
Chemistry of the d-Block Elements
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Alfred Werner – Founder of Coordination Chemistry
CoIIICl3 • 4NH3violetvioleo
CoIIICl3 • 4NH3greenpraseo
CoIIICl3 • 5NH3redpurpureo
CoIIICl3 • 6NH3yellowluteo
ComplexColorPrefix
Chemistry of the d-Block Elements
Hex(a)ammin Cobalt(III) ChlorideCoCl3 • 6NH3
Alfred Werner – Founder of Coordination Chemistry
Chemistry of the d-Block Elements
Alfred Werner‘s Kollektion (8000+ Komplexe!) & die „Katakomben“ an der Universität Zürich
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Alfred Werner – Founder of Coordination Chemistry
NH3—ClCo—NH3—Cl
NH3—NH3—NH3—NH3—Cl
ClCo—NH3—Cl
NH3—NH3—NH3—NH3—Cl
ClCo—Cl
NH3—NH3—NH3—NH3—Cl
ClCo—Cl
NH3—NH3—NH3—Cl
[Co(NH3)6]Cl3
[Co(NH3)5Cl]Cl2
[Co(NH3)4(Cl)2]Cl
[Co(NH3)4(Cl)2]Cl
Jørgensen Werner
2 isomers!
Chemistry of the d-Block Elements
Alfred Werner – Founder of Coordination Chemistry
Chemistry of the d -Block Elements
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Alfred Werner – Leitfähigkeit (Kohlrausch’s Prinzip, Konstitution)
Chemistry of the d-Block Elements
Alfred Werner & Arturo Miolati (1893 – 1896)
Alfred Werner – Isomere (Konfiguration)
Chemistry of the d-Block Elements
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Alfred Werner – Founder of Coordination Chemistry
Chemistry of the d-Block Elements
Alfred Werner – Founder of Coordination Chemistry
Chemistry of the d-Block Elements
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A Sidenote: Serendipity in Chemistry
"Testicular cancer went from a disease that normally killed about 80% of the patients, to one which is close to 95% curable. This is probably the most exciting development in the treatment of cancers that we have had in the past 20 years. It is now the treatment of first choice in ovarian, bladder, and osteogenicsarcoma [bone] cancers as well."
—Barnett Rosenberg, who led the research group that discovered cisplatin, commenting on the impact of cisplatin in cancer chemotherapy
Cisplatin was approved by the FDA for the treatment of genitourinary tumors in 1978.
Since then, Michigan State has collected over $160 million in royalties from cisplatin and a related drug, carboplatin, which was approved by the FDA in 1989 for the treatment of ovarian cancers.
PtNH 3
NH 3
O
O
O
O
carboplatin
Prof. Barnett Rosenberg, MSU(Prof. S.J. Lippard, MIT)
Chemistry of the d-Block Elements
First non-carbon containing chiral compound:
Hexol [(Co ((OH)2Co(NH3)4)3](SO4)3, resolved in 1914with (+)-bromocamphorsulphonate
CoOH
OHHO
OH
H O
H O
Co
Co
Co
NH 3
NH 3
H 3NH 3N
NH 3
NH 3H 3N
NH 3
H 3N
NH 3H 3N
NH 3
O
S
O
OO
Br
6+
definitive proof ofAlfred Werner’s
octahedron model-> Synthesis of optically active
complexes!
Chemistry of the d-Block Elements
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Coordination Chemistry - Nomenclature
Chemistry of the d-Block Elements
Chemistry of the d-Block Elements
Coordination Chemistry - Nomenclature
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Coordination Chemistry - Nomenclature
Chemistry of the d-Block Elements
Coordination Chemistry - Nomenclature
Chemistry of the d-Block Elements
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Coordination Chemistry - Nomenclature
Chemistry of the d-Block Elements
Coordination Chemistry - Nomenclature
Chemistry of the d-Block Elements
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Coordination Chemistry - Nomenclature
Chemistry of the d-Block Elements
Coordination Chemistry - Nomenclature
Chemistry of the d-Block Elements
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Coordination Chemistry - Nomenclature
Chemistry of the d-Block Elements
Coordination Chemistry - Nomenclature
Chemistry of the d-Block Elements
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Coordination Chemistry - NomenclatureIUPAC Rules for complex formula:
• Coordination complex in square brackets, charge superscripted
[CrIII(NCO)4(NH3)2] − [PtIIBrClI(NO2)(NH3)] −
[PtIVBrClI(NO2)(py)(NH3)]
• Central atom in front of ligands
• Anionic in front of neutral ligands
• Multiple atoms & abbrev. ligands in round brackets
• Oxidation number superscripted @ central atom
looks awkward…
I would use
(Br)(Cl)(I)…
abbrev: C5H5N
Chemistry of the d-Block Elements
Coordination Chemistry - NomenclatureIUPAC Rules for complex name:
Main Difference: ligands first, followed by central atomstrictly follow alphabetical order
Dichloro(thiourea)(triphenylphosphine)platinum(II)[PtCl2(py)(NH3)] Amminedichloro(pyridine)platinum(II)
• Ligands in alphabetical order in front of central atom/ion
Specification of oxidation number (Roman numerals) of thecentral atom (or the charge number in Arabic numerals after the name of the central atom)
Name of anionic ligands close with “o”, neutral ligands inround brackets (except: ammine, aqua, carbonyl, nitrosyl)
Chemistry of the d-Block Elements
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Coordination Chemistry - Nomenclature
K3[Fe(CN)6] Potassium-hexacyanoferrate(III) orPotassium-hexacyanoferrate(3-)(or Tripotassium-hexacyanoferrate)
K2[PtCl4] Potassium-tetrachloroplatinate(II)
Na2[Fe(CO)4] Disodium-tetracarbonylferrate
[Co(H2O)2(NH3)4]Cl3 Tetraammindiaquacobalt(3+)chloride
Chemistry of the d-Block Elements
Coordination Chemistry - Nomenclature
[Ni(H2O)(NH3)4]SO4 Tetra(a)mminediaquanickel(II)sulfate
Na2[OsCl5N] Disodium-pentachloronitrido-osmate(VI)
[CoCl(NO2)(NH3)4]Cl Tetra(a)mminechloronitrito-cobalt(III) chloride
[CoCl(NH2)(en)2]NO3 Amidochlorobis(ethylenediamine)cobalt(III) nitrate
[FeH(CO)3(NO)] Tricarbonylhydridonitrosyliron(?)
[PtCl(NH2CH3)(NH3)]Cl Amminchlorobis(methylamine)platinum(II) chloride
Chemistry of the d-Block Elements
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Coordination Chemistry - Nomenclature
RuPPh 3
PPh 3
H
OC
Cl
PPh 3
CoOH 2
NH 3
NC
NC
OH 2
NH 3
CoNH 2
NH 2
NH 2
H 2N
H 2N
H 2N
Ni
CNCN
NC
NC
CN0 +
I I I I I
Carbonylchloro-hydridotris(tri-
phenylphosphine)ruthenium(II)
Diamminediaqua-dicyanocobalt(III)
Tris(ethylenediamine)-cobalt(III) pentacyano-
nickelate(II)
Chemistry of the d-Block Elements
Coordination Chemistry - Isomers
PtNH 3
NH 3
N
HOM
NH 3
Cl
Ph 3P
Br
CO
NMe3
MN
N
N
N
N
N
NH
CH 3CH 3
CH 3
HH 3CH
CH 2H 3CCH 3CH 3
H 3C
1
2
3
3
12
34
5
6
practice…
Priority Rules: …remember Cahn-Ingold-Prelog?
Chemistry of the d-Block Elements
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Coordination Chemistry - Isomers
…in four-coordinate square-planar complexes:
cis- & trans-
and chiral isomers insquare planar complexes
chirality (chiral center) can be incorporated ligand
Chemistry of the d-Block Elements
Coordination Chemistry - Isomers
…in six-coordinate octahedral complexes:
special case of cis- & trans-isomers:
carboxyl grouptrans to tertiary N
carboxyl groupcis to tertiary N
Chemistry of the d-Block Elements
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Coordination Chemistry - Isomers
…in six-coordinate octahedral complexes:
in addition to cis- & trans-and chiral (Chapter 4)isomers:
fac- and mer-isomersmore obvious withpoly (tri-)dentateligands such as:tacn, tp- (fac)or terpy (mer)
N
NN
N
N N
tacn terpy
Chemistry of the d-Block Elements
Coordination Chemistry - Isomers
…in six-coordinate octahedral complexes:
special case of chirality in enor tacn complexes:
NH 2NH 2
N
N N
tacn, δδδ or λλλ en
Chemistry of the d-Block Elements
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Coordination Chemistry - Isomers
Hydrate Isomerism
CrCl3 • 6H2O (dark green, mostly trans-[CrCl2(H2O)4]Cl)
violet [Cr(H2O)6]Cl3
blue-green [CrCl(H2O)5]Cl2 • H2O
dark green [CrCl2(H2O)4]Cl • 2H2O*
yellow-green [CrCl3(H2O)3] in conc. HCl
separation by
cation ion
exchange
chromatography
Chemistry of the d-Block Elements
Coordination Chemistry - Isomers
Ionization Isomerism
[CoCl(NH3)4(H2O)]Br2 and [CoBr2(NH3)4]Cl • H2O (also hydrate isomers)
[Co(SO4)(NH3)5]NO3 and [Co(NO3)(NH3)5]SO4
[CoCl(NO2)(NH3)4]Cl and [CoCl2(NH3)4]NO2
Chemistry of the d-Block Elements
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Coordination Chemistry - Isomers
Coordination Isomerism
[Pt(NH3)4][PtCl4] (Magnus’ green salt)
different metal ions in different oxidation states:
[Co(en)3][Cr(CN)6] and [Cr(en)3][Co(CN)6]
[Pt(NH3)4][PtCl6] and [PtCl2(NH3)4][PtCl4]
Chemistry of the d-Block Elements
Coordination Chemistry - Isomers
Linkage (ambidentate) Isomerism
intramolecular!
Philip CoppensUniversity atBuffalo (NY)
Chemistry of the d-Block Elements
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Coordination Chemistry - Isomers
Linkage (ambidentate) Isomerism
isothiocyanato thiocyanato (1-diphenylphosphine-3-dimethylaminepropane)palladium(II)
free rotation
large steric effect
Chemistry of the d-Block Elements
Coordination Chemistry – Coordination Numbers& Structures
Notes & Blackboard
Chemistry of the d-Block Elements
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Coordination Chemistry – Bonding in TM Complexes
Ligand Fields & Ligand StrengthsHigh-Spin & Low-Spin Complexes
Chemistry of the d-Block Elements
The Metals s-, p-, and d-Orbitals:
taken from: Harvey & Porter “Introduction to Physical Inorganic Chemistry”Addison-Wesley 1963
electron densityon the axes!
electron density in between the axes!
The five d-orbitals
Chemistry of the d-Block Elements
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Approx. dependency of orbitalenergy on atomic number (nuclear charge)Schematic orbital energy diagram
taken from Harvey & Potter “Introduction to PhysicalInorganic Chemistry” Wesley 1963
Chemistry of the d-Block Elements
- Review -
Remember???
For example: Nickel (1s2)(2s22p6)(3s23p6) (4s2) (3d8)
In complexes: [Ni2+] (1s2)(2s22p6)(3s23p6) (3d8) unpaired electrons!!!
For a 3d electron: Z* = Z – SZ*= 28 – [18 x (1.00)] – [7 x (o.35)] = 7.55
(1s, 2s, 2p, 3s, 3p) (3d)
The 18 electrons in the 1s, 2s, 2p, 3s, and 3p levels contribute 1.00each (Rule 3b); the other 7 electrons in 3d contribute 0.35 each,and the 4s electrons do not contribute (Rule 2).
For a 4s electron: Z* = Z – SZ* = 28 – [10 x (1.00)] – [16 x (o.85)] – [1 x (0.35)]
(1s, 2s, 2p) (3s, 3p, 3d) (4s)
Z* = 28 – 23.95 = 4.05 The 4s electrons are held less tightly than the 3d!
All transition metals loose ns electrons more readily than (n – 1)d electron:Ti(III): d1, V(III): d2, Mn(II): d5, Mn(III): d4, Mn(IV): d3, Mn(V): d2
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Coordination Chemistry – Magnetism
Chemistry of the d-Block Elements
A) Measurement of Susceptibility by Faraday’s MethodB) Measurement of Magnetization with a SQUID Magnetometer
Principle: In an inhomogeneous field a paramagnetic sampleis attracted into the zone with the largest field; a diamagneticsample is repulsed.
Coordination Chemistry – paired/unpaired d-electrons & magnetism
Chemistry of the d-Block Elements
Measurement of Susceptibility by Faraday’s Method
dF = ½ μ0(χ – χmed)grad(H2)dv
Fz = μ0(χ – χmed)vH dH/dzin vacuum or helium:
Fz = μ0χg m H(dH/dz) + F’
standard with known χg* and m*
χM = χg* [m* / (Fz* - F’)][Fz – F’)/m] M0
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Chemistry of the d-Block Elements
Coordination Chemistry – molecular magnetism
Chemistry of the d-Block Elements
Coordination Chemistry – molecular magnetism
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Chemistry of the d-Block Elements
Coordination Chemistry – molecular magnetism
Coordination Chemistry – Bonding in TM ComplexesLigand Fields & Ligand Strengths
High-Spin & Low-Spin Complexes
Chemistry of the d-Block Elements
• Shape and Symmetry of Ligand and Metal Orbitals
• d-Orbital Splitting in Transition Metal Complexes:
1) Nature of the ligand
2) Symmetry of the Complex
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Chemistry of the d-Block Elements
Introduction - History
G. N. Lewis16. Febr. 1901 – 19. Aug. 1994
Nevil Vincent Sidgwick05. Mai. 1873 – 15. März 1952
Chemistry of the d-Block Elements
Lewis Acid-Base Concept:
• Formation of Complexes via Ion-Ion and/or Ion-Dipole Forces:
Fe2+ + 4 Cl− [FeCl4]−
ion - ion
δ+ δ−
Fe2+ + 6 H2O [Fe(OH2)6]2+
ion - dipole
e-hole e-pair adduct
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Chemistry of the d-Block Elements
Lewis Acid-Base Concept:
• Formation of Complexes via Ion-Ion and/or Ion-Dipole Forces:
Fe2+ + 6 |CN− [Fe(CN)6]4−
ion - ion
Why not just 5 CN- ?
3d64s04p0 + 6 x 2 3d104s24p6 : 18 e- Krypton e-configuration
same with Fe(CO)5 but plenty of exceptions to the rule K3[Fe(CN)6] (17e), [FeCl4]− (13e), ...
Chemistry of the d-Block Elements
Linus Pauling16. Febr. 1901 – 19. Aug. 1994
Valence-Bond Theory
in Chemistry (1954)"for his research into the nature of the chemical bond and its application to theelucidation of the structure of complex substances"
Nobel Peace Price (1962)
only individual in history to have won two unshared Nobel Prizes
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Chemistry of the d-Block Elements
Valence-Bond Theory
Chemistry of the d-Block Elements
Shortcomings of the Valence-Bond Theory
1) Fails to predict magnetic properties (unpaired electrons)e.g.: i) all Co(III) Complexes are diamagnetic; except [CoF6]3-, [CoF3(H2O)3]
ii) Cr(III) in Oh: 3 unpaired e−; Cr(II) in Oh: predicted: 2e−, exp.: 4 unpaired e−
2) Ni(II) planar vs. octahedral is supposed to introduce change from covalent to ionice.g.: [Ni(en)2]2+ 2NH3 [Ni(NH3)2(en)2]
3) Two Atomic Orbitals (AOs) produce MO(bonding) and MO(antibonding)
4) Color of Transition Metal Complexes! E.g.: [Ti(H2O)6]3+ λmax = 490 nm
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Chemistry of the d-Block Elements
Crystal Field Theory
Hans Bethe (PhD in theor. physics)2. Juli 06 – 06. März 05 ;=)
Electrostatic Model:
M+ + L− [M—L]
Underlying Principles:
♦ Ligand-Field Strength♦ Asymmetric part of the electron interaction♦ Spin-Orbit Splitting
Chemistry of the d-Block Elements
σ - Symmetrical Metal-Ligand Interaction:
taken from: Harvey & Porter “Introduction to Physical Inorganic Chemistry” Addison-Wesley 1963
Note Symmetry of Orbitals!s = gp = ud = gf = u
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Chemistry of the d-Block Elements
Shortcomings of the Crystal-Field Theory
1) Ligands are not negatively charged hard spheres2) Many complexes with significantly covalent bonds
Chemistry of the d-Block Elements
Molecular Orbital Theory
Friedrich Hund04. Febr. 1896 – 31. März 1997
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Chemistry of the d-Block Elements
Molecular Orbital Theory
Erich Hückel1896 - 1980
Robert S. Mulliken1896 - 1986
Chemistry of the d-Block Elements
Molecular Orbital Theory
1) Considers IONIC as well as COVALENT bonding
2) Here: No Mathmatical but Phenomenological Considerations
3) MO Theory Contains Aspects of Valence-Bond (VB-) and Crystal-Field Theory
Molecular Orbitals (MOs) are formed via Linar Combination of Atomic Orbitals (AOs)
metal centerorbital basis: 5 x nd - orbitals1 x (n+1)s - orbital3 x (n+1)p - orbitals
combines with ligand
valence orbitalsCan be s, p, or spn
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Chemistry of the d-Block Elements
Molecular Orbital Theory
1) Only orbitals with same symmetry interact (e.g.: M=O or M≡O?)
2) For optimal interaction, energy difference should not be too large (e.g.: H-H, H-Cl, NaCl)
3) The better the overlap, the better the orbital combination ( see 2. and distance)
Chemistry of the d-Block Elements
Molecular Orbital Theory
taken from Riedel „Moderne Anorganische Chemie“ 2. Auflage
six σ-orbitals arranged for an octahedral complex (σ-Interactions only)
not covered in this lecture…try at home!
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Chemistry of the d-Block Elements
MO Theory
CF
VBHow is Δo (in σ-complexes)
explained in terms of MO-Theory?
metal d-orbitals ligand
orbitals
MO Diagramfor octhaedral (Oh)σ−only complexes
Chemistry of the d-Block Elements
Molecular Orbital Theory
taken from Cotton, Wilkinson, Gaus „Grundlagen der Anorganischen Chemie“, VCH Verlag
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Chemistry of the d-Block Elements
Molecular Orbital Theory
taken from Cotton, Wilkinson, Gaus „Grundlagen der Anorganischen Chemie“, VCH Verlag
Chemistry of the d-Block Elements
Molecular Orbital Theory
large ΔE between M and L orbitals
• weak orbital interaction• small d-splitting (ligand field Δo)
small ΔE between M and L orbitals
• strong orbital interaction• large d-splitting (ligand field Δo)
ΔE ΔE
Cl− vs F−
H3N vs H2OH2O vs H2S
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Chemistry of the d-Block Elements
Molecular Orbital Theory
Introduction of metal-ligand π−Interaction:
Chemistry of the d-Block Elements
Molecular Orbital Theory
full σ-donororbital
empty π-acceptororbital
full σ-donororbital
full π-donororbital
Stabilization
Destabilization
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Chemistry of the d-Block Elements
Molecular Orbital Theory
Interpretation of the Spectrochemical Series in Terms of MO Theory
weak ligands strong ligandshigh-spin complexes low-spin complexes
strong π-donor< weak π-donor < pure σ-donor < weak π-acceptor < strong π-acceptor
I− < Br− < S2− < SCN− < Cl− < NO3− < F−< OH− <
H2O < NCS− < CH3CN < NH3 < en < bpy < phen <
NO2− < CN− < PR3 < CO
Chemistry of the d-Block Elements
H2, alkanesDonation of electrons from filled d-orbitals of metal to empty σ*-orbitals of liganddπ—σ*
CO, RNC, pyridine, CN-, N2, NO2
-, ethylene
Donation of electrons from filled d-orbitals of metal to empty π* (antibonding)-orbitals of ligand
dπ—π*
R2S (R3P, R3As)Donation of electrons from filled d-orbitals of metal to empty d-orbitals of liganddπ—dπ
RO-, RS-, F-, Cl-, R2N-
Donation of electrons from filled p-orbitals of ligand to empty d-orbitals of metalpπ—dπ
Ligand examplesDescriptionType
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Molecular - Orbital Diagram for Octahedral Complexes (σ - only)
Chemistry of the d-Block Elements
Chemistry of the d-Block Elements
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Chemistry of the d-Block Elements
Geometry (Symmetry) Dependence of Ligand—Field Splitting (cont’d):
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Geometry (Symmetry) Dependence of Ligand—Field Splitting (cont’d):
A Case Study: The Electronic Structure of Hemoglobin/Myoglobin:
A Case Study: The Electronic Structure of Hemoglobin/Myoglobin:
NN
N
Observation: Diamagnetic Spin Ground State for the Oxy-Formof Hemoglobin/Myoglobin!
…with FeIII (S = 1/2 or 5/2) and 3O2 (S = 1)???
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Observation: Diamagnetic Spin Ground State for the Oxy-Form!
A Case Study: The Electronic Structure of Hemoglobin/Myoglobin:
Solution A:
Observation: Diamagnetic Spin Ground State for the Oxy-Form!
A Case Study: The Electronic Structure of Hemoglobin/Myoglobin:
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Solution B:
Observation: Diamagnetic Spin Ground State for the Oxy-Form!
A Case Study: The Electronic Structure of Hemoglobin/Myoglobin: