Table of Contents 1
Chapter 1 Review on the Structural Chemistry of the M-M'-S Complexes(M=Mo,W;M′=Cu,Ag) 1
1.1 Introduction 1
1.2 Structural Chemistry of the Discrete Molybdenum(Tungsten)-Copper(Silver)-Sulfur Compounds 4
1.2.1 Binuclear Compounds 5
1.2.2 Trinuclear Compounds 5
1.2.3 Tetranuclear Compounds 8
1.2.4 Pentanuclear Compounds 13
1.2.5 Hexanuclear Compounds 14
1.2.6 Heptanuclear Compounds 16
1.2.7 Octanuclear Compounds 17
1.2.8 Oligonuclear Compounds 21
1.3 Structural Chemistry of the Polymeric Molybdenum(Tungsten)-Copper(Silver)-Sulfur Compounds 25
Chapter 2 Synthetic Experiments and Discussion 35
2.1 Synthetic Experiments 35
2.1.1 Starting Materials for Experiments 35
2.1.2 The System of the Larger Molybdenum(Tungsten)-Copper-Sulfur Compounds 36
2.1.2.1 Preparation of[Et4N]4[W4Cu4S12O4] 36
2.1.2.2 Preparation of[Et4N]4[Mo4Cu4S12O4] 36
2.1.2.3 Preparation of[W4Cu4S12O4(CuTMEN)4] 37
2.1.2.4 Preparation of[Mo4Cu4S12O4(CuTMEN)4] 37
2.1.2.6 Preparation of[Et4N]4[W8Cu12S28O4]·DMF 38
2.1.2.5 Preparation of[Et4N]4[Mo8Cu12S28O4]·DMF 38
2.1.3 The System of the Polymeric Tungsten-Silver-Sulfur Compounds 39
2.1.3.1 Preparation of[(W2Ag2S8)·(TMENH2)·(TMEN)·(H2O)]n 39
2.1.3.2 Preparation of[WAgS4·NH4]n 40
2.1.3.3 Preparation of[WS4Ag·HNEt3·DMF]n 40
2.1.3.4 Preparation of[WS4Ag·NH3C(CH2OH)3·2DMF]n 40
2.1.3.5 Preparation of[WS4Ag·NH3C(CH2OH)3·H2O]n 41
2.1.3.6 Preparation of[W3S12Ag3·Nd(DMSO)8]n 41
2.1.3.7 Preparation of[W4S16 Ag4·2Ca(DMSO)6]n 41
2.1.3.10 Preparation of[W4Ag5S16·Pr(DMF)8]n 42
2.1.3.9 Preparation of[W4Ag5S16·La(DMF)8]n 42
2.1.3.8 Preparation of[W4Ag5S16·Nd(DMF)8]n 42
2.1.3.11 Preparation of[W4Ag5S16·Eu(DMF)8]n 43
2.1.3.12 Preparation of[W4Ag5S16·Ce(DMF)8]n 43
2.1.3.13 Preparation of[(CH3)2N(CH)2(CH)2N(CH3)2]n[S2WS2Ag]n 43
2.2 Discussion of the Syntheses 44
2.2.1 Larger M-Cu-S Cluster Complexes(M=Mo,W) 44
2.2.2 Polymeric W-Ag-S Complexes 46
Chapter 3 Structural Determination and Discussion 52
3.1 Crystal Structural Determination 52
[W4Cu4S12O4] 63
3.2.1.1 Structure of the Octanuclear Cluster[Et4N]4· 63
3.2 Description of the Crystal Structures 63
3.2.1 The System of the Larger Heterometallic M-Cu-S Clusters Containing a Square-type Unit{M4 Cu4 S12}(M=Mo,W) 63
3.2.1.2 Structure of the Octanuclear Cluster[Et4 N]4·[Mo4Cu4S12O4] 67
3.2.1.3 Structure of the Dodecanuclear Cluster[W4Cu4S12O4(CuTMEN)4] 67
3.2.1.4 Structure of the Dodecanuclear Cluster[Mo4Cu4S12O4(CuTMEN)4] 71
3.2.1.5 Structure of the Eicosanuclear Cluster[Et4N]4·[Mo8Cu12S28O4]·DMF 71
3.2.1.6 Structure of the Eicosanuclear Cluster[Et4N]4·[W8Cu12S28O4]·DMF 74
3.2.2 The System of One-dimensional Heterometallic W-Ag-S Polymeric Cluster Complexes 75
3.2.2.1 Structure of the Linear Chain Complex[(W2Ag2S8)·(TMENH2)·(TMEN)·(H2O)]n 75
3.2.2.2 Structure of the Linear Chain Complex[WAgS4·NH4]n 79
3.2.2 3 Structure of the Linear Chain Complex[WS4Ag·HNEt3·DMF]n 81
3.2.2.4 Strcture of the Linear Chain Complex[WS4Ag·NH3C(CH2OH)3·2DMF]n 83
3.2.2.5 Structure of the Double Chain Complex[WS4Ag·NH3C(CH2OH)3·H2O]n 85
3.2.2.6 Structure of the Helical Chain Complex[W3S12Ag3·Nd(DMSO)8]n 88
3.2.2.7 Structure of the Zigzag Chain Complex[W4S16Ag4·2Ca(DMSO)6]n 92
3.2.2.8 Structure of the One-dimensional Chain Complex[W4Ag5S16·Nd(DMF)8]n 96
3.2.2.9 Structure of[(CH3)2N(CH)2(CH)2N(CH3)2]n·[S2WS2Ag]n 102
4.1.2 Electronic Spectra 108
4.1.1 Vibration Spectra 108
4.1.3 NMR Spectra 108
Chapter 4 Spectral Determination and Discussion 108
4.1 Spectral Determination 108
4.2 Discussion of the Spectra 109
4.2.1 Vibration Spectra 109
4.2.1.1 IR Spectra 109
4.2.1.2 Raman Spectra 112
4.2.2 Electronic Spectra 112
4.2.3 NMR Spectra 114
4.2.3.1 95Mo NMR Spectra 114
4.2.3.2 1H and 13C NMR Spectra 116
5.1 Preparation of Compounds 121
Chapter 5 EXAFS Studies on a Novel Iron-Copper-Sulfur Cluster 121
5.2 Collection of the EXAFS Data 122
5.3 Data Analysis 124
5.4 Results and Discussion 129
Chapter 6 Summary and Prospect 136
Acknowledgments 139
References 141
Appendix 149
A1 Publication List 149
A2 Tables of Atomic Coordinates and Geometrical Paramenters 155
A3 IR and Raman Spectra 225