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Chapter 7 d-Metal Complexes D epartment of Chemistry 學習化學的五個基礎面向 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 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 1827 Discovery of Zeise Salt KPtCl3C2H4 What’s the structure of the Zeise Salt? Cl K+ Cl PtII CH2 Cl CH2 1913 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 Alfred Werner 1866 – 1919 University of Zurich Zurich, Switzerland http://nobelprize.org/chemistry/laureates/1913/ http://www.aci.unizh.ch/coord/aw.html Complex Color CoCl3·6NH3 Yellow Old Name IUPAC Name luteo complex hexaamminecobalt(III) Chloride CoCl3·5NH3 Purple purpureo complex Pentaamminechlorocobalt(III) chloride CoCl3·4NH3 Green praseo complex trans-tetraamminedichlorocobalt(III) chloride CoCl3·4NH3 violet violeo complex trans-tetraamminedichlorocobalt(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 Coordination number = 3 [Cu(CN)2]Cl [Cu(CN)2]Cl [Cu(CN)2]Cl [Complexes of C60 Acetylactonate (acac) Coordination number = 4 A tetrahedral structure may lack of perpendicular C2 symmetry [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]3tbp sqp tbp sqp Hexamethyltren(CoIII) heme tbp sqp Berry pseudo-rotation tbp sqp tbp Site preference: For electron-rich center, the pacids might prefer the equatorial sites, but this is not a rigid rule. [Re(S2C2Ph2)3] [Re(S2Prism C2Ph2and )3] trigonal antiprism Trigonal [Re(SEther Crown 2C2Ph2)3] [CoIII(edta)]– (hexadentate) Pentagonal bipyramidal [Zr(ox)4 4] 4] [Zr(ox)4 From cubic to Trigonal dodecahedron And square antiprism (a) Na7Zr6F31 square antiprism [Zr(ox)4 4] (b) [Zr(acac)2](NO3)2 dodecahedron (c) MoAs82- [ReH9]2- Tricapped trigonal prism [Ce(NO3)6 2] Metal Clusters [Re2Cl8 2] [Fe4S4(SPh)4 2] [Re2Cl8]2First 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