chapter 7 d -metal complexes
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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
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