Chapter 7 d -Metal Complexes

1. Chapter 7d-Metal Complexes

2. 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

3. 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

4. 1827 Discovery of Zeise Salt KPtCl3C2H4 What’s the structure of the Zeise Salt?

5. 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/chemistry/laureates/1913/ http://www.aci.unizh.ch/coord/aw.html

6. Complex CoCl3·6NH3 CoCl3·5NH3 CoCl3·4NH3 CoCl3·4NH3 Color Yellow Purple Green violet 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

7. Werner’s experiments for the conductivity of some coordination complexes

8. Werner’s experiments for the conductivity of some coordination complexes

9. polyhedron structures

10. Ionic radius ratio is crucial (sometimes critical) to the geometry. Huheey pp.473

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

12. Linkage isomers

14. [Mn(OH2)6]SO4

15. [Mo(CN)8]3-

20. Coordination number = 1

21. Coordination number = 2

22. Hg(CH3)2

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

24. [Cu(CN)2]Cl

25. [Cu(CN)2]Cl

26. [Complexes of C60

27. Acetylactonate (acac)

28. Coordination number = 4 A tetrahedral structure may lack of perpendicular C2 symmetry

29. [PtCl2(NH3)2] Square Planar Cis-form trans-form

30. [PtCl(dien)]+ Pincer ligand

31. heme

32. coenzymeB12

33. chlorophyll

34. chloroplastmodel charge transfer

35. heme tbp sqp

36. [Ni(CN)5]3- tbp sqp

37. tbp sqp

38. Hexamethyltren(CoIII)

39. heme tbp sqp

40. Berry pseudo-rotation tbp sqp tbp

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

44. [Re(S2C2Ph2)3]

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

46. [Re(S2C2Ph2)3] Crown Ether

47. [CoIII(edta)]–(hexadentate)

48. Pentagonal bipyramidal

49. [Zr(ox)4]4-

50. [Zr(ox)4]4- From cubic to Trigonal dodecahedron And square antiprism