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 Elementsmy personal favorites

9. Chemistry of the d -Block Elements

The d - Block Elementsmy personal favorites

Prof. Karl Wieghardt Max-Planck-Institute for Bioinorganic Chemistry Muelheim/Germany

9. Chemistry of the d -Block Elements

Alfred Werner Founder of Coordination Chemistry
Dot Representation: Pentachlorophosphorous PCl5 PCl3 Cl2 Copper(II) Sulfate Pentahydrate CuSO4 5H2O

Hex(a)ammin Cobalt(III) Chloride CoCl3 6NH3

9. Chemistry of the d -Block Elements

Alfred Werner Founder of Coordination Chemistry

Prefix luteo purpureo praseo violeo

Color yellow red green violet

Complex CoIIICl3 6NH3 CoIIICl3 5NH3 CoIIICl3 4NH3 CoIIICl3 4NH3

9. Chemistry of the d -Block Elements

Alfred Werner Founder of Coordination Chemistry
Jrgensen NH3Cl CoNH3Cl NH3NH3NH3NH3Cl Cl CoNH3Cl NH3NH3NH3NH3Cl Cl CoCl NH3NH3NH3NH3Cl Cl CoCl NH3NH3NH3Cl Werner [Co(NH3)6]Cl3

[Co(NH3)5Cl]Cl2

[Co(NH3)4(Cl)2]Cl

2 iso m s! er

[Co(NH3)4(Cl)2]Cl

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

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
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 Prof. Barnett Rosenberg, MSU from cisplatin and a (Prof. S.J. Lippard, MIT) related drug, carboplatin, which was approved by the FDA in 1989 for the "Testicular cancer went from a disease that normally treatment of ovarian killed about 80% of the patients, to one which is close to cancers. 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

O Pt O

NH3 NH3

O carboplatin

9. Chemistry of the d -Block Elements

Alfred Werner Founder of Coordination Chemistry

9. Chemistry of the d -Block Elements

First non-carbon containing chiral compound:

Hexol [(Co ((OH)2Co(NH3)4)3](SO4)3, resolved

with (+)-bromocamphorsulphonate
O Br O H3 N O S O NH3 H3N Co NH3 H O O H NH3 H3 N HO Co HO H3 N Co H3N Co OH OH NH3 NH3 NH3 NH3

in 1914

6+
definitive proof of Alfred Werners octahedron model -> Synthesis of optically active complexes!

9. Chemistry of the d -Block Elements

Coordination Chemistry - Nomenclature

9. Chemistry of the d -Block Elements

Coordination Chemistry - Nomenclature

9. Chemistry of the d -Block Elements

Coordination Chemistry - Nomenclature

9. Chemistry of the d -Block Elements

Coordination Chemistry - Nomenclature

9. Chemistry of the d -Block Elements

Coordination Chemistry - Nomenclature

9. Chemistry of the d -Block Elements

Coordination Chemistry - Nomenclature

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]

lo I ok w sa (B o r) uld wk (C u w l) se ard (I )

[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
abbrev: C5H5N

9. Chemistry of the d -Block Elements

Coordination Chemistry - Nomenclature
IUPAC Rules for complex name: Main Difference: ligands first, followed by central atom strictly 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 the central atom (or the charge number in Arabic numerals after the name of the central atom) Name of anionic ligands close with o, neutral ligands in round 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) or Potassium-hexacyanoferrate(3-) (or Tripotassium-hexacyanoferrate) Potassium-tetrachloroplatinate(II) Disodium-tetracarbonylferrate

K2[PtCl4] Na2[Fe(CO)4]

[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 Na2[OsCl5N] [CoCl(NO2)(NH3)4]Cl [CoCl(NH2)(en)2]NO3 [FeH(CO)3(NO)] [PtCl(NH2CH3)(NH3)]Cl

Tetra(a)mminediaquanickel(II) sulfate Disodium-pentachloronitridoosmate(VI) Tetra(a)mminechloronitritocobalt(III) chloride Amidochlorobis(ethylenediamine) cobalt(III) nitrate Tricarbonylhydridonitrosyliron(?) Amminchlorobis(methylamine) platinum(II) chloride

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9. Chemistry of the d -Block Elements

Coordination Chemistry - Nomenclature
Diamminediaquadicyanocobalt(III)
Cl OC H Ru PPh3 PPh3 0 NC NC Co OH2 NH3 OH2 + H N H2 2 N III NH2 Co NC NH2 N NC H2 H2N CN Ni
II

CN CN

PPh3

NH3

Carbonylchlorohydridotris(triphenylphosphine) ruthenium(II)

Tris(ethylenediamine)cobalt(III) pentacyanonickelate(II)

9. Chemistry of the d -Block Elements

Coordination Chemistry - Isomers
Priority Rules: remember Cahn-Ingold-Prelog? practice 6 CO 1 Br
Ph3P M N N H3C N H N M N

1 HO 2 N
Pt

3 NH3
NH3 3

2 Cl
NH3

H CH3 N CH 3 N H CH3

NMe3 4

H3C CH2

H3C CHCH3 3

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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 in square 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- & transisomers:

carboxyl group trans to tertiary N

carboxyl group cis 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- & transand chiral (Chapter 4) isomers:

N N N N N N

tacn

terpy

fac- and mer-isomers more obvious with poly (tri-)dentate ligands such as: tacn, tp- (fac) or terpy (mer)

9. Chemistry of the d -Block Elements

Coordination Chemistry - Isomers
in six-coordinate octahedral complexes: special case of chirality in en or tacn complexes:

N N N NH2 en NH2

tacn, or

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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)
by i on at on ar i hy n sep g e rap tio ca han tog c a ex rom ch

violet blue-green dark green

[Cr(H2O)6]Cl3 [CrCl(H2O)5]Cl2 H2O [CrCl2(H2O)4]Cl 2H2O*

yellow-green [CrCl3(H2O)3] in conc. HCl

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 [CoCl(NO2)(NH3)4]Cl and [Co(NO3)(NH3)5]SO4 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 [Pt(NH3)4][PtCl6] and [Cr(en)3][Co(CN)6] [PtCl2(NH3)4][PtCl4]

9. Chemistry of the d -Block Elements

Coordination Chemistry - Isomers
Linkage (ambidentate) Isomerism

in tr a

ol ec u la

r!

Philip Coppens University at Buffalo (NY)

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9. Chemistry of the d -Block Elements

Coordination Chemistry - Isomers
Linkage (ambidentate) Isomerism

free rotation large steric effect

isothiocyanato thiocyanato (1-diphenylphosphine-3dimethylaminepropane)palladium(II)

9. Chemistry of the d -Block Elements

Coordination Chemistry Coordination Numbers & Structures

Chapter 10 Coordination Chemistry Bonding in TM Complexes Ligand Fields & Ligand Strengths High-Spin & Low-Spin Complexes Chapter 16 Coordination Chemistry Some exciting bioinorganic case studies

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