Chapter 7 d-Metal Complexes

C hemistry

D epartmentof

Get acquainted with chemical language 熟習化學語言

Constitute basic concepts and modeling 建構概念與模型

Quantity and analysis 量與計算

Thinking with and through operation 操作型思考

Data bank of descriptive and applied knowledge 敘述化學與知識應用

學習化學的五個基礎面向

d-Metal ComplexesContents

I Structure & Symmetry

1 Constitution

2 Representatitive ligands & Nomenclature

3 Isomerism & Chirality

II Bonding & Electronic Structure

1 Crystal Field Theory

2 The Electronic Structures of Four Coordinate Complexes

3 Ligand Field Theory

III Reactions of Complexes

1 Coordination Equilibria

2 Rates & Mechanisms of Ligands

1827 Discovery of Zeise Salt

KPtCl3C2H4

What’s the structure of the Zeise Salt?

PtII

Cl Cl

Cl

CH2

CH2

K+

19131913

Alfred Werner1866 – 1919 University of Zurich Zurich, Switzerland

http://nobelprize.org/chemistry/laureates/1913/

http://www.aci.unizh.ch/coord/aw.html

in recognition of his work on the linkage of atoms in molecules by which he has thrown new light on earlier investigations and opened up new fields of research especially in inorganic chemistry

Color

Yellow

Purple

Green

violet

Complex

CoCl3·6NH3

CoCl3·5NH3

CoCl3·4NH3

CoCl3·4NH3

Old Name

luteo complex

purpureo complex

praseo complex

violeo complex

IUPAC Name

hexaamminecobalt(III)Chloride

Pentaamminechloro-cobalt(III) chloride

trans-tetraammine- dichlorocobalt(III) chloride

trans-tetraammine- dichlorocobalt(III) chloride

Werner’s experiments for the conductivity of some coordination complexes

Werner’s experiments for the conductivity of some coordination complexes

polyhedron structures

Ionic radius ratio is crucial (sometimes critical) to the geometry.

Huheey pp.473

(H3N)5Cr-O-Cr(NH3)5

Linkage isomers

[Mn(OH2)6]SO4

[Mo(CN)8]3-

Coordination number = 1

Coordination number = 2

Hg(CH3)2

[Cu(CN)2]Cl Coordination number = 3

[Cu(CN)2]Cl

[Cu(CN)2]Cl

[Complexes of C60

Acetylactonate (acac)

A tetrahedral structure may lack of perpendicular C2 symmetry

Coordination number = 4

[PtCl2(NH3)2] Square Planar

Cis-form trans-form

[PtCl(dien)]+

Pincer ligand

heme

coenzymeB12

chlorophyll

chloroplastmodel

charge transfer

heme

tbp sqp

[Ni(CN)5]3-

tbp

sqp

tbp sqp

Hexamethyltren(CoIII)

heme

tbp sqp

Berry pseudo-rotation

tbp sqp tbp

Site preference: For electron-rich center, the -acids might prefer the equatorial sites, but this is not a rigid rule.

[Re(S2C2Ph2)3]

[Re(S2C2Ph2)3]Trigonal Prism and trigonal antiprism

[Re(S2C2Ph2)3]Crown Ether

[CoIII(edta)]– (hexadentate)

Pentagonal bipyramidal

[Zr(ox)4]4-

[Zr(ox)4]4-

From cubic to Trigonal dodecahedron And square antiprism

[Zr(ox)4]4-

(a) Na7Zr6F31

square antiprism

(b) [Zr(acac)2](NO3)2

dodecahedron

(c) MoAs82-

[ReH9]2- Tricapped trigonal prism

[Ce(NO3)6]2-

[Re2Cl8]2-

Metal Clusters

[Fe4S4(SPh)4]2-

[Re2Cl8]2-

First M-M quadriple bond

Eclipsed structure

[Re2Cl8]2-

crown ether

C. J. Pedersen

cryptate

J.-M. Lehn

carcerand

D. J. Cram

Degined

ligand

Self assembling

helix

Supramolecules