Chemistry of Ruthenium (eBook)

Front Cover 1
The Chemistry of Ruthenium 4
Copyright Page 5
Table of Contents 27
Dedication 6
Frontispiece 9
Preface 10
ABBREVIATIONS 13
SIGN CONVENTIONS AND CONVERSION FACTORS 26
CHAPTER 1. INTRODUCTION 42
1.1 Scope and vera causa 42
1.2 Ordering of the chapters 43
1.3 Ordering within the chapters 44
1.4 Discovery and early history of ruthenium 44
1.5 Extraction and purification of ruthenium 49
1.6 Analysis 49
1.7 Applications and uses of ruthenium 49
1.8 Isotopes of ruthenium 51
1.9 Physical properties of ruthenium 51
1.10 Chemical properties of ruthenium 52
CHAPTER 2. OXIDATION STATE 56
2.1 What is oxidation state? 56
2.2 Does oxidation state have a chemical significance? 58
2.3 The MLX system 61
2.4 MLX plots 69
2.5 Mössbauer spectroscopy 77
CHAPTER 3. RUTHENIUM(VIII) 84
3.1 Ruthenium(VIII) fluoride 84
3.2 Ruthenium(VIII) oxide 84
CHAPTER 4. RUTHENIUM(VII) 98
4.1 Potassium ruthenate(VII) 98
4.2 Sodium ruthenate(VII) 102
4.3 µ-Oxo-bis[trioxo(l,lO-phenanthroline)ruthenium(VII)] 102
CHAPTER 5. RUTHENIUM(VI) 104
5.1 Ruthenium(VI) fluoride 104
5.2 Ruthenium(VI) oxide tetrafluoride 104
5.3 Potassium octafluororuthenate(VI) 105
5.4 Dioxoruthenium(VI) complexes 105
5.5 Nitridoruthenium(VI) complexes 109
5.6 Ruthenium(VI) oxide 112
5.7 Metal ruthenates(VI) 112
5.8 Ruthenium(VI) sulphates and related species 114
5.9 Ruthenium(VI) amides 115
Addenda 116
CHAPTER 6. RUTHENIUM (V) 118
6.1 Ruthenium(V) fluoride 118
6.2 Metal hexafluororuthenates(V) 119
6.3 Non-metal hexafluororuthenates 123
6.4 Bis(tricarbonyldifluororuthenium(II)-ruthenium(V) fluoride 125
6.5 Caesium tetracyanobis(^socyanato)oxoruthenate(V) 126
6.6 Ruthenium(V) oxide 126
6.7 Quaternary ruthenium(V) oxides 126
6.8 Sodium and lithium ruthenates(V) 128
Addenda 129
CHAPTER 7. RUTHENIUM(IV) 132
7.1 Ruthenium(IV) halides and oxohalides 132
7.2 Hexahaloruthenates(IV) 133
7.3 µ-OXO-bis[pentahaloruthenates(IV)] and related complexes 138
7.4 µ-Nitrido-bis[aquatetrahaloruthenates(IV)] and related complexes 142
7.5 Adducts of ruthenium(IV) halides and related complexes 147
7.6 Aqueous chemistry and halo-aqua complexes of ruthenium(IV) 149
7.7 Ruthenium(IV) oxide 154
7.8 Metal ruthenates(IV) 157
7.9 Ruthenium(IV) chalcogenides 174
7.10 Ruthenium(IV) nitrates, sulphates, carboxylates and related species 176
7.11 Ruthenium(IV) hydrides 180
7.12 Ruthenium(IV) allyl complexes 184
7.13 Ruthenium(IV) cyclopentadienyl complexes 189
7.14 Mixed oxidation state (IV/III) complexes 190
Addenda 194
CHAPTER 8. RUTHENIUM(III) 196
8.1 Ruthenium(III) halides 196
8.2 Hexahaloruthenates(III) and related complexes 202
8.3 Ruthenium(III) halo-aqua systems 207
8.4 Hexaaquaruthenium(III) 214
8.5 Ruthenium(III) oxide and metal ruthenates(III) 214
8.6 Ruthenium(III) carboxylates 216
8.7 Nitro, nitrato and sulphato complexes of ruthenium(III) 240
8.8 ß-Diketonate complexes of ruthenium(III) and related complexes 241
8.9 Ruthenium(III) complexes with oxygen-donor ligands 247
8.10 Ruthenium(III) complexes with sulphur-donor ligands 248
8.11 Thio and dithio-ß-diketonate complexes of ruthenium(III) and related complexes 253
8.12 Ruthenium dithiocarboxylates and related complexes 255
8.13 Tris(dithiocarbamato)ruthenium(III) and related complexes 255
8.14 Hexaamineruthenium(III) salts 262
8.15 Halopentaammineruthenium(III) salts and related complexes 270
8.16 Dihalotetraammineruthenium(III) salts and related complexes 284
8.17 Trihalotriammineruthenium(III) complexes and related compounds 286
8.18 [(NH3)5RuL]3+ and [ (NH3) (4RuL2]3+ salts and related species 286
8.19 1,2-Diaminoethane complexes of ruthenium(III) and related species 299
8.20 Other amine complexes of ruthenium(III) 304
8.21 2,2'-Bipyridine and 1,10-phenanthroline complexes of ruthenium(III 309
8.22 Phosphine and arsine complexes of ruthenium(III) 325
8.23 Ruthenium(III) cyanides, thiocyanates and azides 341
8.24 Ruthenium(III) carbonyl complexes 343
8.25 Ruthenium(III) organometallic chemistry 348
8.26 Catalytic activation of molecular hydrogen by ruthenium(III) 348
8.27 Mixed oxidation state (III/II) complexes 351
Addenda 376
CHAPTER 9. RUTHENIUM(II) 382
9.1 Ruthenium(II) halides 382
9.2 Ruthenium(II) halide complexes 383
9.3 Hexaaquaruthenium(II) 391
9.4 Ruthenium(II) oxide 392
9.5 ß-Diketonate complexes of ruthenium(II) 393
9.6 Sulphoxide complexes of ruthenium(II) 394
9.7 Ruthenium(II) complexes with sulphide ligands 400
9.8 Dithiocarbamate complexes of ruthenium(II) 400
9.9 Dithiolene, thiol and thione complexes of ruthenium(II) 403
9.10 Hexaammineruthenium(II) salts 407
9.11 Halopentaammineruthenium(II) salts and related species 409
9.12 Dihalotetraammineruthenium(II) salt 411
9.13 [Ru(NH3)5L]2+ and [Ru(NH3)4L2]2+ salts and related species 411
9.14 1,2-Diaminoethane complexes of ruthenium(II) and related species 428
9.15 Ruthenium(II) complexes with other N-donor ligands 430
9.16 Dinitrogen complexes of ruthenium(II) 437
9.17 2,2'-Bipyridine and 1,10-phenanthroline complexes of ruthenium(II) 455
9.18 Ruthenium(II) phthalocyanine and porphyrin complexes 517
9.19 Haloruthenium(II) phosphine and arsine complexes 528
9.20 Hydridoruthenium(II) phosphine and arsine complexes 571
9.21 Ruthenium(II) phosphine and arsine complexes with other secondary ligands 592
9.22 Halocarbonylruthenium(II) complexes 648
9.23 Hydridocarbonylruthenium(II) complexes 701
9.24 Ruthenium(II) cyanides 709
9.25 Isonitrile complexes of ruthenium(II) 712
9.26 Carbene complexes 721
9.27 Cycloruthenated complexes 729
9.28 Alkyl-, acyl- and aryl- ruthenium(II) phosphine and arsine complexes 746
9.29 Fluoroalkene complexes and related species 755
9.30 Allyl complexes 761
9.31 Diene complexes 768
9.32 Bis(n5-cyclopentadienyl)ruthenium(II) (ruthenocene) and its derivatives 791
9.33 Mono(n5-cyclopentadienyl)ruthenium(II) derivatives 819
9.34 Cyclohexadienyl complexes 852
9.35 Bis(arene)ruthenium(II) salts and related species 855
9.36 Monomeric mono(arene)ruthenium(II) complexes 862
9.37 Oligomeric (arene)ruthenium(II) complexes 881
9.38 Cycloheptadienyl, cycloheptatrienyl and cycloheptatriene complexes 889
9.39 Cyclooctadienyl, cyclooctatrienyl, cyclooctatetraene and pentalene complexes 899
9.40 Complexes with Group IVB donor ligands 908
9.41 Carbaborane complexes of ruthenium(II) 927
9.42 Complexes with Group IIB donor ligands 927
9.43 Ruthenium(II) hydrides 929
9.44 Mixed oxidation state (I1/0) complexes 929
Addenda 931
CHAPTER 10. RUTHENIUM(I) 932
10.1 Ruthenium(I) halides 932
10.2 Ruthenium(I) bipyridine complexes 932
10.3 Ruthenium(I) phosphine and arsine complexes 932
10.4 Ruthenium(I) cyanides 933
10.5 Ruthenium(I) carbonyl halides 933
10.6 Ruthenium(I) carbonyl carboxylates 933
10.7 Ruthenium(I) carbonyl complexes with chalcogenide ligands 937
10.8 Ruthenium(I) carbonyl phosphine complexes 938
10.9 Ruthenium(I) silyl, germyl and stannyl complexes 941
10.10 Ruthenium(I) carbonyl hydrides 943
10.11 Acyclic alkene complexes 943
10.12 Allyl complexes 945
10.13 Cyclopentadienyl complexes 946
10.14 Cycloheptatrienyl complexes 958
10.15 Cyclooctatetraene and cyclooctatriene derivatives 960
10.16 Bicyclo derivatives 965
Addenda 966
CHAPTER 11. RUTHENIUM(O) 968
11.1 Ruthenium(O) carbonyls 968
11.2 Ruthenium(O) phosphine complexes 971
11.3 Ruthenium(O) carbonyl phosphine complexes 972
11.4 Ruthenium(O) complexes with nitrogen-donor ligands 984
11.5 Ruthenium(O) isonitrile complexes 985
11.6 Alkene complexes 986
11.7 Alkyne complexes 992
11.8 Diene complexes 992
11.9 Arene complexes 1001
11.10 Cycloheptatriene complexes 1007
11.11 Cyclooctatetraene and cyclooctatriene complexes 1008
11.12 Anionic complexes 1013
Addenda 1013
CHAPTER 12. LOW OXIDATION STATES 1016
12.1 Sodium tetracarbonylruthenate(-II) 1016
12.2 Potassium tetrakis(trifluorophosphine)ruthenate(-II) 1017
CHAPTER 13. RUTHENIUM CARBONYL CLUSTERS 1018
13.1 Unsubstituted carbonyl cluster compound 1018
13.2 Hydridocarbonyl cluster compounds 1029
13.3 Carbidocarbonyl clusters 1043
13.4 Halocarbonyl clusters 1045
13.5 Group VIB derivatives 1046
13.6 Nitrene, amine and nitrosyl derivatives 1053
13.7 Phosphine and arsine derivatives of ruthenium carbonyls 1060
13.8 Ethylidene, ylid, methylene and germylene derivatives 1078
13.9 Alkyne derivatives 1082
13.10 Alkene derivative 1094
13.11 Allyl derivatives 1100
13.12 Cyclopentadienyl derivatives 1114
13.13 Arene derivatives 1115
13.14 Cycloheptatriene derivatives 1117
13.15 Cyclooctatetraene derivatives 1119
13.16 Bicyclo derivatives 1124
13.17 Mixed-metal clusters 1133
Addenda 1142
CHAPTER 14. RUTHENIUM NITROSYLS 1146
14.1 Ruthenium nitrosyl halides 1146
14.2 Halo(nitrosyl)ruthenates 1147
14.3 Aquahalo(nitrosyl)ruthenium complexes, and related hydroxo derivatives 1151
14.4 Aqua and hydroxo complexes of (nitrosyl)ruthenium 1155
14.5 Nitro and nitrato complexes of (nitrosyl)ruthenium 1156
14.6 Complexes of (nitrosyl)ruthenium with anionic and neutral oxygen-donor ligands 1161
14.7 Dioxygen complexes of (nitrosyl)ruthenium 1167
14.8 Complexes of (nitrosyl)ruthenium with sulphur- and selenium-donor ligands 1169
14.9 Ammine(nitrosyl)ruthenium complexes 1171
14.10 Amine and nitrile complexes of (nitrosyl)ruthenium 1179
14.11 Phosphine, arsine and stibine complexes of (nitrosyl)ruthenium 1179
14.12 Phosphine complexes of hydrido(nitrosyl)ruthenium 1189
14.13 Carbonyl complexes of (nitrosyl)ruthenium 1191
14.14 Pentacyano(nitrosyl)ruthenate(2-) and related species 1194
14.15 Organometallie complexes 1195
14.16 (Nitrosyl)ruthenium complexes with Group IVB donor ligands 1200
14.17 Dinitrosyl ruthenium complexes 1201
14.18 Arylazo and aryldiimine complexes 1203
CHAPTER 15. PH0T0PHYSICS AND PHOTOCHEMISTRY OF TRIS(DIIMINE)RUTHENIUM(II) COMPLEXES 1214
15.1 Luminescence of tris(2,2'-bipyridine)ruthenium(II) complexes and relatedspecies 1214
15.2 Electronic absorption spectra of tris(2,2'-bipyridine)ruthenium(II) andrelated species 1234
15.3 ELECTRONIC ABSORPTION AND EMISSION SPECTRA OF MIXED-LIGAND COMPLEXES 1250
15.4 Spectral properties of {[Ru(bipy)3]2+}* and the efficiency of intersystem crossing 1255
15.5 Photolabilisation and photochemistry of [Ru(bipy)3] and relatedcomplexes 1257
15.6 Redox potentials of excited states and electrogenerated chemiluminescence 1259
15.7 Quenching reactions 1262
15.8 Photocatalytic decomposition of water 1281
Addenda 1299
REFERENCES 1302
ADDENDA REFERENCES 1358
INDEX 1378