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9. Chemistry of the d -Block Elements
The d - Block Elements
http://www.chemsoc.org/viselements/pages/pertable_fla.htm
9. Chemistry of the d -Block Elements
The d - Block Elements…my personal favorites
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9. Chemistry of the d -Block Elements
The d - Block Elements…my personal favorites
Prof. Karl WieghardtMax-Planck-Institutefor Bioinorganic ChemistryMuelheim/Germany
9. Chemistry of the d -Block Elements
Alfred Werner – Founder of Coordination Chemistry
“Dot” Representation:
Pentachlorophosphorous PCl5PCl3 • Cl2
Copper(II) Sulfate PentahydrateCuSO4 • 5H2O
Hex(a)ammin Cobalt(III) ChlorideCoCl3 • 6NH3
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9. Chemistry of the d -Block Elements
Alfred Werner – Founder of Coordination Chemistry
CoIIICl3• 4NH3violetvioleo
CoIIICl3• 4NH3greenpraseo
CoIIICl3• 5NH3redpurpureo
CoIIICl3• 6NH3yellowluteo
ComplexColorPrefix
9. Chemistry of the d -Block Elements
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!
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9. Chemistry of the d -Block Elements
Alfred Werner – Founder of Coordination Chemistry
9. Chemistry of the d -Block Elements
Alfred Werner – Founder of Coordination Chemistry
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9. Chemistry of the d -Block Elements
Alfred Werner – Founder of Coordination Chemistry
9. Chemistry of the d -Block Elements
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 osteogenic sarcoma [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.
PtNH3
NH3
O
O
O
O
carboplatin
Prof. Barnett Rosenberg, MSU(Prof. S.J. Lippard, MIT)
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9. Chemistry of the d -Block Elements
Alfred Werner – Founder of Coordination Chemistry
First non-carbon containing chiral compound:
Hexol [(Co ((OH)2Co(NH3)4)3](SO4)3, resolved in 1914with (+)-bromocamphorsulphonate
CoOH
OHHO
OH
HO
HO
Co
Co
Co
NH3
NH3
H3N
H3N
NH3
NH3H3N
NH3
H3N
NH3H3N
NH3
O
S
O
OO
Br
6+
9. Chemistry of the d -Block Elements
definitive proof ofAlfred Werner’s
octahedron model-> Synthesis of optically active
complexes!
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9. Chemistry of the d -Block Elements
Coordination Chemistry - Nomenclature
9. Chemistry of the d -Block Elements
Coordination Chemistry - Nomenclature
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9. Chemistry of the d -Block Elements
Coordination Chemistry - Nomenclature
9. Chemistry of the d -Block Elements
Coordination Chemistry - Nomenclature
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9. Chemistry of the d -Block Elements
Coordination Chemistry - Nomenclature
9. Chemistry of the d -Block Elements
Coordination Chemistry - Nomenclature
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9. Chemistry of the d -Block Elements
Coordination Chemistry - Nomenclature
9. Chemistry of the d -Block Elements
Coordination Chemistry - Nomenclature
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9. Chemistry of the d -Block Elements
Coordination Chemistry - Nomenclature
9. Chemistry of the d -Block Elements
Coordination Chemistry - Nomenclature
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9. Chemistry of the d -Block Elements
Coordination Chemistry - Nomenclature
IUPAC 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
9. Chemistry of the d -Block Elements
Coordination Chemistry - Nomenclature
IUPAC 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)
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9. Chemistry of the d -Block Elements
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 Tetra(a)mmindiaquacobalt(3+)chloride
9. 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
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9. Chemistry of the d -Block Elements
Coordination Chemistry - Nomenclature
RuPPh3
PPh3
H
OC
Cl
PPh3
CoOH2
NH3
NC
NC
OH2
NH3
CoNH2
NH2
NH2
H2N
H2N
H2N
Ni
CNCN
NC
NC
CN0 +
III II
Carbonylchloro-hydridotris(tri-
phenylphosphine)ruthenium(II)
Diamminediaqua-dicyanocobalt(III)
Tris(ethylenediamine)-cobalt(III) pentacyano-
nickelate(II)
9. Chemistry of the d -Block Elements
Coordination Chemistry - Isomers
PtNH3
NH3
N
HOM
NH3
Cl
Ph3P
Br
CO
NMe3
MN
N
N
N
N
N
NH
CH3CH3
CH3
HH3CH
CH2H3CCH3CH3
H3C
1
2
3
3
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5
6
practice…
Priority Rules: …remember Cahn-Ingold-Prelog?
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9. Chemistry of the d -Block Elements
Coordination Chemistry - Isomers
…in four-coordinate square-planar complexes:
cis- & trans-
and chiral isomers insquare planar complexes
chirality (chiral center) can be incorporated ligand
9. 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
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9. Chemistry of the d -Block Elements
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
9. Chemistry of the d -Block Elements
Coordination Chemistry - Isomers
…in six-coordinate octahedral complexes:
special case of chirality in enor tacn complexes:
NH2
NH2
N
N N
tacn, δδδ or λλλ en
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9. Chemistry of the d -Block Elements
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
separa
tion by
cation
ion
excha
nge
chrom
atogra
phy
9. 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
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9. Chemistry of the d -Block Elements
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]
9. Chemistry of the d -Block Elements
Coordination Chemistry - Isomers
Linkage (ambidentate) Isomerism
intramolecular!
Philip CoppensUniversity atBuffalo (NY)
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9. Chemistry of the d -Block Elements
Coordination Chemistry - Isomers
Linkage (ambidentate) Isomerism
isothiocyanato thiocyanato (1-diphenylphosphine-3-dimethylaminepropane)palladium(II)
free rotation
large steric effect
9. Chemistry of the d -Block Elements
Coordination Chemistry – Coordination Numbers& Structures
Chapter 10Coordination Chemistry – Bonding in TM Complexes
Ligand Fields & Ligand StrengthsHigh-Spin & Low-Spin Complexes
Chapter 16Coordination Chemistry – Some exciting bioinorganic
case studies
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