chemistry of the d -block elements - inorganic chemistry cdm... · 3 chemistry of the d -block...

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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


History:

PdNH3

NH3

H3N

H3NPd

Cl

Cl

Cl

Cl

CoIII

CN

CN

NC

NC

NC

CNLouis Nicolas Vauquelin1813

Gmelin1822

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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)


Newest generation:

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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 - )





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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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.


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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Another success story at the HEART of coordination chemistry:Cardiolite


The d - Block Elements

http://www.chemsoc.org/viselements/pages/pertable_fla.htm

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The d - Block Elements…my personal favorites


The d - Block Elements…my personal favorites

Prof. Karl WieghardtMax-Planck-Institutefor Bioinorganic ChemistryMuelheim/Germany


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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



Copper(II) Acetate HydrateCu(CH3COO)2 • H2O



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CoIIICl3 • 4NH3violetvioleo

CoIIICl3 • 4NH3greenpraseo

CoIIICl3 • 5NH3redpurpureo

CoIIICl3 • 6NH3yellowluteo

ComplexColorPrefix




NH3—ClCo—NH3—Cl

NH3—NH3—NH3—NH3—Cl

ClCo—NH3—Cl


ClCo—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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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)


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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!


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Coordination Chemistry - Nomenclature


9. 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


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)


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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



[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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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)


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?


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…in four-coordinate square-planar complexes:

cis- & trans-

and chiral isomers insquare planar complexes

chirality (chiral center) can be incorporated ligand



…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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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




special case of chirality in enor tacn complexes:

NH 2NH 2

N

N N

tacn, δδδ or λλλ en


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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



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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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]



Linkage (ambidentate) Isomerism

intramolecular!

Philip CoppensUniversity atBuffalo (NY)


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Linkage (ambidentate) Isomerism

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

free rotation

large steric effect


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


chemistry of the d -block elements - inorganic chemistry cdm... · 3 chemistry of the d -block...

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