Chapter 7 d-Metal Complexes

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• Chapter 7 d-Metal Complexes

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• Get acquainted with chemical language
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• d-Metal Complexes
• Contents
• 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

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• 1827 Discovery of Zeise Salt
• KPtCl3C2H4
• Whats the structure of the Zeise Salt?

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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
1913
Alfred Werner 1866 1919 University of Zurich
Zurich, Switzerland http//nobelprize.org/chemi
stry/laureates/1913/ http//www.aci.unizh.ch/coord
/aw.html
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Color Yellow Purple Green violet
Complex CoCl36NH3 CoCl35NH3 CoCl34NH3 Co
Cl34NH3
Old Name luteo complex purpureo
complex praseo complex violeo complex
IUPAC Name hexaamminecobalt(III) Chloride Pentaa
mminechloro- cobalt(III) chloride
trans-tetraammine- dichlorocobalt(III)
chloride trans-tetraammine- dichlorocobalt(III)
chloride
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Werners experiments for the conductivity of
some coordination complexes
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Werners experiments for the conductivity of
some coordination complexes
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polyhedron structures
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Ionic radius ratio is crucial (sometimes
critical) to the geometry.
Huheey pp.473
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(H3N)5Cr-O-Cr(NH3)5
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Linkage isomers
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Mn(OH2)6SO4
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Mo(CN)83-
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Coordination number 1
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Coordination number 2
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Hg(CH3)2
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Cu(CN)2Cl
Coordination number 3
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Cu(CN)2Cl
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Cu(CN)2Cl
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Complexes of C60
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Acetylactonate (acac)
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Coordination number 4
A tetrahedral structure may lack of perpendicular
C2 symmetry
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PtCl2(NH3)2 Square Planar
Cis-form trans-form
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PtCl(dien)
Pincer ligand
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heme
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coenzymeB12
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chlorophyll
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chloroplastmodel
charge transfer
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heme
tbp sqp
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Ni(CN)53-
tbp
sqp
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tbp sqp
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Hexamethyltren(CoIII)
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heme
tbp sqp
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Berry pseudo-rotation
tbp sqp tbp
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Site preference For electron-rich center, the
p-acids might prefer the equatorial sites, but
this is not a rigid rule.
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Re(S2C2Ph2)3
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Re(S2C2Ph2)3
Trigonal Prism and trigonal antiprism
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Re(S2C2Ph2)3
Crown Ether
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CoIII(edta) (hexadentate)
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Pentagonal bipyramidal
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Zr(ox)44-
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Zr(ox)44-
From cubic to Trigonal dodecahedron And square
antiprism
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Zr(ox)44-

1. Na7Zr6F31 square antiprism(b)
   Zr(acac)2(NO3)2 dodecahedron (c) MoAs82-

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ReH92-
Tricapped trigonal prism
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Ce(NO3)62-
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Re2Cl82-
Metal Clusters
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Fe4S4(SPh)42-
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Re2Cl82- First M-M quadriple bond
Eclipsed structure
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Re2Cl82-
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crown ether
C. J. Pedersen
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cryptate
J.-M. Lehn
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carcerand
D. J. Cram
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Deginedligand
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Self assembling helix
Supramolecules