Chemistry of Precious Metals - CNTQ

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vi Contents 1.8.4 Sulphide and Sulphoxide Complexes ............. 39 1.8.5 Nitrosyl Complexes ........................................ 43 1.8.6 Porphyrin Complexes .................................... 48 1.8.7 EDTA Complexes .......................................... 50 1.8.8 Other Complexes of Ruthenium ..................... 52 1.9 Complexes of Ruthenium(IV) .......................................... 53 1.10 Complexes of Osmium(0) ............................................... 54 1.11 Osmium Complexes in Oxidation States (II-IV) ............... 54 1.11.1 Ammine Complexes ...................................... 54 1.11.2 Tertiary Phosphine Complexes ...................... 57 1.11.3 Carboxylate Complexes ................................. 66 1.11.4 Nitrosyl Complexes ........................................ 66 1.11.5 Other Osmium Complexes ............................. 68 1.12 Compounds in High Oxidation States ............................. 68 1.12.1 Compounds of the MO2 2+ Groups ................... 69 1.12.2 Nitride Complexes ......................................... 72 1.12.3 Imides ........................................................... 74 1.13 Simple Alkyls and Aryls ................................................... 75 2. Rhodium and Iridium .................................................... 78 2.1 Introduction ..................................................................... 78 2.2 The Elements and Uses .................................................. 78 2.2.1 Extraction ...................................................... 79 2.3 Halides and Halide Complexes ....................................... 79 2.3.1 Rhodium Halides ........................................... 79 2.3.2 Iridium Halides .............................................. 80 2.3.3 Halometallates .............................................. 81 2.4 Oxides, Hydrides and Other Binary Compounds ............ 85 2.5 Aqua Ions and Simple Salts ............................................ 87 This page has been reformatted by Knovel to provide easier navigation.
This page has been reformatted by Knovel to provide easier navigation. Contents vii 2.6 Compounds of Rhodium(0) ............................................. 88 2.7 Compounds of Rhodium(I) .............................................. 88 2.7.1 Tertiary Phosphine Complexes ...................... 89 2.7.2 Carbonyl Complexes ..................................... 98 2.7.3 Alkene Complexes ......................................... 104 2.7.4 Isocyanide Complexes ................................... 105 2.8 Rhodium(II) Complexes .................................................. 106 2.8.1 Phosphine Complexes ................................... 106 2.8.2 Dimers .......................................................... 107 2.8.3 Other Complexes .......................................... 114 2.9 Rhodium(III) Complexes ................................................. 115 2.9.1 Complexes of O-Donors ................................ 115 2.9.2 Complexes of Ammines ................................. 116 2.9.3 Complexes of Other N-Donors ....................... 121 2.9.4 Complexes of S-Donors ................................. 123 2.9.5 Tertiary Phosphine Complexes ...................... 125 2.10 Iridium (I) Complexes ...................................................... 132 2.10.1 Tertiary Phosphine Complexes ...................... 132 2.10.2 Vaska's Compound ........................................ 135 2.11 Dioxygen Complexes ...................................................... 142 2.12 Iridium(II) Complexes ...................................................... 145 2.13 Iridium(III) Complexes ..................................................... 145 2.13.1 Complexes of Ammines ................................. 146 2.13.2 Complexes of S-Donors ................................. 147 2.13.3 Tertiary Phosphine and Arsine Complexes .................................................... 148 2.13.4 Hydride Complexes ....................................... 149 2.13.5 Case Study of Dimethylphenylphosphine Complexes .................................................... 152
Page 1 and 2: Chemistry of Precious Metals Dr S.A
Page 3 and 4: Preface Some 20 years ago, I was pr
Page 5 and 6: Abbreviations acac acetylacetonate,
Page 7: Contents Preface ..................
Page 11 and 12: This page has been reformatted by K
Page 13 and 14: This page has been reformatted by K
Page 15 and 16: 30O 0 C. Powdered osmium is slowly
Page 17 and 18: Figure 1.1 The tetrameric structure
Page 19 and 20: ReCl5 structure (Os-Cl = 2.24 A (te
Page 21 and 22: (a) (b) Figure 1.3 The structure Of
Page 23 and 24: Oxidation state H-5 Fluorination of
Page 25 and 26: Os(terpy)Cl3 Os(phen)2Cl2 + Os(py)2
Page 27 and 28: Table 1.5 Bond lengths (A) in dipyr
Page 29 and 30: In the case of ruthenium, the Ru2X9
Page 31 and 32: Figure 1.10 The three-centre molecu
Page 33 and 34: L4.1 Anions Alkalis reduce RuO4 to
Page 35 and 36: The ruthenium(IV) aqua ion, best ma
Page 37 and 38: its inertness (e.g. high temperatur
Page 39 and 40: All the trihalides are known to hav
Page 41 and 42: Table 2.2 Vibrational fundamentals
Page 43 and 44: Figure 2.3 103 Rh NMR spectrum of m
Page 45 and 46: 2.5 Aqua ions and simple salts Aqua
Page 47 and 48: 2.7.7 Tertiary phosphine complexes
Page 49 and 50: Figure 2.7 The solid-state 31 P NMR
Page 51 and 52: The reaction with MeI proceeds in t
Page 53 and 54: Rh(PPh3)3(NH3) + Rh(PPh3)/ Rh(PPh3)
Page 55 and 56: It has an approximately square plan
Page 57 and 58: Rh2(CO)4Cl2 (L = RNH2, py) (L = R2s
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RhCl3(CO)(PPh3)2 RhHCl2(CO)(PPh3)2
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Figure 2.25 31 P NMR spectrum of ^H
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Figure 2.29 The structure of RhBr((
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A more unusual complex is formed by
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Figure 2.35 The 'lantern' structure
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Intensity Wa ven umber/cm" 1 Figure
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In the MO scheme the rhodium atoms
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A number of rhodium(III) complexes
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Table 3.1 lonization energies (kJ m
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Table 3.2 Characteristics of pallad
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Pt (hot wire) 525 0 C, in vacuo sea
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Figure 3.4 The chain structure adop
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Table 3.4 Bond lengths in MX^" (A)
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Table 3.7 Comparative vibrational d
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Tertiary hydrides can be made [38,
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Hydrated palladium perchlorate has
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(conveniently measured in terms of
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Figure 3.14 Zerovalent complexes of
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Figure 3.17 A comparison between th
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and platinum compounds do not exist
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Figure 3.20 A palladium(I) 2-diphen
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4 Silver and gold 4.1 Introduction
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Neither metal is attacked by oxygen
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Table 4.4 Characteristics of silver
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magnetic moment (1.07/xB) owing to
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Figure 4.3 The structure OfAuCl2. T
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Au(OH)4. There have been claims for
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4.6 Silver(I) complexes 4.6.1 Compl
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Figure 4.9 The dimeric structure ad
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Figure 4.11 The structure of [Ag8(S
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ieff = 2.2 /XB; gj| = 2.11, g_L = 2
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Table 4.8 Au-P bond lengths in the
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Table 4.10 Bond lengths (A) in the
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the anion in Ph4As + Au(SPh)2 [95]
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Index This index is divided by elem
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Index terms Links Gold(I) complexes
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Index terms Links This page has bee
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Index terms Links Halides This page
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Index terms Links Iridium(IV) compl
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Index terms Links Vibrational spect
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Index terms Links Hydride complexes
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Page 143 and 144:
Index terms Links Halide complexes
Page 145 and 146:
Index terms Links Palladium(IV) com
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Index terms Links Bond lengths (Con
Page 149 and 150:
Index terms Links Platinum(II) comp
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Index terms Links Platinum(IV) comp
Page 153 and 154:
Index terms Links Bond lengths (Con
Page 155 and 156:
Page 157 and 158:
Index terms Links Rhodium(III) comp
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Page 161 and 162:
Index terms Links Magnetic properti
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Index terms Links Ruthenium(III) co
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Index terms Links Chemical vapour d
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References Chapter 1 1. W.P. Griffi
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47. RJ.H. Clark, M.L. Franks and P.
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102. F.A. Cotton, L. Labella and M.
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148. P.P. Dwyer and J.W. Hogarth, J
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195. J.R. Wolf, G.C. Bazan and R.R.
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42. Refs 3(d) and 6, p. 906. 43. (a
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98. Ref. 6, p. 975; Inorg. Synth.,
Page 181 and 182:
144. M.P. Yagupsky and G. Wilkinson
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