Chemistry

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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

12

34

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