This volume of Inorganic Syntheses spans the preparations of wide range of important inorganic, organometallic and solid-state compounds. The volume is divided into 6 chapters. The first chapter contains the syntheses of some key early transition metal halide clusters and the very useful mononuclear molybdenum(III) synthon, Mo Cl3(THF)3. Chapter 2 covers the synthesis of a number of cyclopentadienyl compounds, including a novel route to sodium and potassium cyclopentadienide, MC5H5. Chapter 3 details synthetic procedures for a range of metal-metal bonded compounds, including several with metal-metal multiple bonds. Chapter 4 contains procedures for a range of early and late transition metal compounds, each a useful synthon for further synthetic elaboration. Chapter 5 deals with the synthesis of a number of main group compounds and ligands, while Chapter 6 covers teaching laboratory experiments.
Cuprins
Preface v
Dedication vii
Notice to Contributors and Checkers xv
Toxic Substances and Laboratory Hazards xvii
Chapter One TRANSITION METAL HALIDE COMPOUNDS 1
1. Octahedral Hexatantalum Halide Clusters 1
A. Tetradecachlorohexatantalum Octahydrate 3
B. Tetradecabromohexatantalum Octahydrate 4
C. Tetrakis(benzyltributylammonium) Octadecachlorohexatantalate 5
2. Octahedral Hexamolybdenum Halide Clusters 8
A. Tetradecachlorohexamolybdate Hexahydrate (Chloromolybdic Acid) 10
B. Hexamolybdenum Dodecachloride 12
3. Ether Complexes of Molybdenum(III) and Molybdenum(IV) Chlorides 15
A. Tetrachlorobis(diethyl ether)molybdenum(IV) 16
B. Trichlorotris(tetrahydrofuran)molybdenum(III) 17
4. Octahedral Hexatungsten Halide Clusters 19
A. Bis(hydroxonium) Tetradecachlorohexatungstate Heptahydrate (Chlorotungstic Acid) 21
B. Hexatungsten Dodecachloride 22
5. Trinuclear Tungsten Halide Clusters 24
A. Tritungsten Decachloride 26
B. Trisodium Tridecachlorotritungstate 27
C. Tris(benzyltributylammonium) Tridecachlorotritungstate 28
6. Crystalline and Amorphous Forms of Tungsten Tetrachloride 30
A. Crystalline Tungsten Tetrachloride by Solid-State Reduction 32
B. Amorphous Tungsten Tetrachloride by Solution-Phase Reduction 33
Chapter Two CYCLOPENTADIENYL COMPOUNDS 35
7. Sodium and Potassium Cyclopentadienide 35
A. Sodium Cyclopentadienide 36
B. Potassium Cyclopentadienide 37
8. (Pentafluorophenyl)cyclopentadiene and its Sodium Salt 38
A. (Pentafluorophenyl)cyclopentadiene 39
B. Sodium (Pentafluorophenyl)cyclopentadienide 41
9. Bis(η5-pentamethylcyclopentadienyl) Complexes of Scandium 42
A. Bis(η5-pentamethylcyclopentadienyl)chloroscandium 43
B. Bis(η5-pentamethylcyclopentadienyl)methylscandium 44
C. Bis(η5-pentamethylcyclopentadienyl)phenylscandium 45
D. Bis(η5-pentamethylcyclopentadienyl)(o-tolyl)scandium 46
10. Bis(η5-pentamethylcyclopentadienyl) Complexes of Titanium, Zirconium, and Hafnium 47
A. Bis(η5-pentamethylcyclopentadienyl)dichlorotitanium(IV) 47
B. Bis(η5-pentamethylcyclopentadienyl)dichlorozirconium(IV) 49
C. Bis(η5-pentamethylcyclopentadienyl)dichlorohafnium(IV)50
11. Bis(η5-pentamethylcyclopentadienyl) Complexes of Niobium and Tantalum 52
A. Bis(η5-pentamethylcyclopentadienyl)dichlorotantalum(IV) 53
B. Bis(η5-pentamethylcyclopentadienyl)dichloroniobium(IV) 55
12. Bis(η5-pentamethylcyclopentadienyl) Complexes of Molybdenum 58
A. Bis(pentamethylcyclopentadienyl)dichloromolybdenum(IV) 59
B. Bis(pentamethylcyclopentadienyl)dihydridomolybdenum(IV) 61
13. (η5-Cyclopentadienyl)tricarbonylmanganese(I) Complexes 62
A. (η5-Cyclopentadienyl)tricarbonylmanganese(I) 63
B. (η5-Pentamethylcyclopentadienyl)tricarbonylmanganese(I) 63
14. 1, 10-Diaminoferrocene 65
A. 1, 10-Dilithioferrocene N, N, N0, N0-Tetramethylethylenediamine 66
B. 1, 10-Dibromoferrocene 67
C. One-Pot Preparation of 1, 10-Dibromoferrocene from Ferrocene 68
D. 1, 10-Diaminoferrocene 69
E. 1, 10-Diaminoferrocenium Hexafluorophosphate 70
F. 1, 10-Diaminoferrocenium Triflate 71
15. Mono(η5-pentamethylcyclopentadienyl) Complexes of Osmium 72
A. Bromoosmic Acid 74
B. Bis(η5-pentamethylcyclopentadienyl)tetrabromodiosmium(III) 75
C. (η5-Pentamethylcyclopentadienyl)(1, 5-cyclooctadiene)-bromoosmium(II) 76
Chapter Three COMPOUNDS WITH METAL–METAL BONDS 78
16. Tetra(acetato)dimolybdenum(II) 78
17. Supramolecular Arrays Based on Dimolybdenum Building Blocks 81
A. Tetrakis(N, N0-di-p-anisylformamidinato)dimolybdenum(II) 84
B. Tris(N, N0-di-p-anisylformamidinato)di(chloro)-dimolybdenum(II, III) 86
C. cis-Bis(N, N0-di-p-anisylformamidinato)tetrakis(acetonitrile)-dimolybdenum(II) Bis(tetrafluoroborate) 87
D. (μ2-Succinato)bis[tris(N, N0-di-p-anisylformamidinato)-dimolybdenum(II)] 88
E. (μ2-η2, η2-Molybdato)bis[tris(N, N0-di-p-anisylformamidinato)-dimolybdenum(II)] 89
F. (μ2-N, N0-Diphenylterephthaloyldiamidato)bis[tris(N, N0-di-panisylformamidinato) dimolybdenum(II)] 90
G. Molecular Propeller: (μ3-Trimesate)tris[tris(N, N0-di-panisylformamidinato) dimolybdenum(II)] 91
H. Molecular Loop: closo-Bis(μ2-malonato)bis[bis(N, N0-di-panisylformamidinato) dimolybdenum(II)] 92
I. Molecular Triangle: closo-Tris(μ2-eq, eq-1, 4-cyclohexanedicarboxylato) tris[bis(N, N0-di-p-anisylformamidinato)-dimolybdenum(II)]92
J. Molecular Square: closo-Tetrakis(μ2-oxalato)tetrakis[bis(N, N0-di-p-anisylformamidinato)dimolybdenum(II)] 93
K. Molecular Cage: closo-Tetrakis(μ3-trimesate)hexakis[bis(N, N0-di-p-anisylformamidinato)dimolybdenum(II)] 94
18. Dimolybdenum and Ditungsten Hexa(alkoxides) 95
A. Hexa(tert-butoxy)dimolybdenum(III) 96
B. Hexakis(2-trifluoromethyl-2-propoxy)dimolybdenum(III) 97
C. Sodium Heptachloropentakis(tetrahydrofuran)ditungstate(III) 98
D. Hexa(tert-butoxy)ditungsten(III) 99
E. Hexakis(2-trifluoromethyl-2-propoxy)ditungsten(III) 100
19. Linear Trichromium, Tricobalt, Trinickel, and Tricopper Complexes of 2, 20-Dipyridylamide 102
A. Dichlorotetrakis(2, 20-dipyridylamido)trichromium(II) 103
B. Dichlorotetrakis(2, 20-dipyridylamido)tricobalt(II) 104
C. Dichlorotetrakis(2, 20-dipyridylamido)trinickel(II) 105
D. Dichlorotetrakis(2, 20-dipyridylamido)tricopper(II) 106
E. Bis(acetonitrile)tetrakis(2, 20-dipyridylamido)trichromium(II) Bis(hexafluorophosphate) 107
F. Bis(acetonitrile)tetrakis(2, 20-dipyridylamido)tricobalt(II) Bis(hexafluorophosphate) 108
G. Bis(acetonitrile)tetrakis(2, 20-dipyridylamido)trinickel(II) Bis(hexafluorophosphate) 108
20. Bis(tetrabutylammonium) Octachloroditechnetate(III) 110
A. Tetrabutylammonium Pertechnetate(VII) 111
B. Tetrabutylammonium Oxotetrachlorotechnetate(V) 112
C. Bis(tetrabutylammonium) Octachloroditechnetate(III) 112
21. Diruthenium Formamidinato Complexes 114
A. Chlorotris(acetato)(N, N0-di-2, 6-xylylformamidinato)-diruthenium(II, III) 115
B. trans-Chlorobis(acetato)bis(N, N0-di-2, 6-xylylformamidinato)-diruthenium(II, III) 117
C. cis-Chlorobis(acetato)bis(N, N0-di-p-anisylformamidinato)-diruthenium(II, III) 118
D. Chloro(acetato)tris(N, N0-di-p-anisylformamidinato)-diruthenium(II, III) 119
E. Chlorotetrakis(N, N0-di-p-anisylformamidinato)-diruthenium(II, III) 120
22. Heptacarbonyl(disulfido)dimanganese(I) 122
23. Di(carbido)tetracosa(carbonyl)decaruthenate(2–) Salts 124
A. Calcium Di(carbido)tetracosa(carbonyl)decaruthenate(2–) 124
B. Bis[bis(triphenylphosphoranylidene)ammonium] Di(carbido)tetracosa(carbonyl)decaruthenate(2–) 125
Chapter Four GENERAL TRANSITION METAL COMPOUNDS 127
24. Bis(1, 2-bis(dimethylphosphano)ethane)tricarbonyltitanium(0) and Hexacarbonyltitanate(2–) 127
A. Bis(1, 2-bis(dimethylphosphano)ethane)-tricarbonyltitanium(0) 129
B. Bis[18-crown-6)(acetonitrile)potassium] Hexacarbonyltitanate(2–) 131
25. Tungsten Benzylidyne Complexes 134
A. Trichloro(1, 2-dimethoxyethane)benzylidynetungsten(VI) 135
B. Chloro Bis[1, 2-bis(diphenylphosphino)ethane]-benzylidynetungsten(IV) 136
26. Tungsten Oxytetrachloride and (Acetonitrile)tetrachlorotungsten Imido Complexes 138
A. Tungsten Oxytetrachloride 139
B. (Acetonitrile)tetrachloro(phenylimido)tungsten(VI) 140
C. (Acetonitrile)tetrachloro(2-propylimido)tungsten(VI) 141
D. (Acetonitrile)tetrachloro(2-propenylimido)tungsten(VI) 142
27. Tungsten Oxytetrachloride and Several Tungstate Salts 143
A. Tungsten Oxytetrachloride 144
B. Bis(tetrabutylammonium) Hexapolytungstate 145
C. Di(cetylpyridinium) Peroxoditungstate 146
D. Bis(tetrabutylammonium) Phenylphosphonatodiperoxotungstate 147
28. Bromotricarbonyldi(pyridine)manganese(I) 148
29. Bis(tetraethylammonium) fac-Tribromotricarbonylrhenate(I) and -Technetate(I) 149
A. Bis(tetraethylammonium) fac-Tribromotricarbonylrhenate(I) 151
B. Bis(tetraethylammonium) fac-Trichlorotricarbonyltechnetate(I) 152
30. Methyl(oxo)rhenium(V) Complexes with Chelating Ligands 155
A. Methyl(oxo)(1, 2-ethanedithiolato)rhenium(V) Dimer 156
B. Methyl(oxo)bis(2-oxyquinoline)rhenium(V) 157
C. Methyl(oxo)(2, 20-thiodiacetato)(triphenylphosphine)-rhenium(V) 158
31. Hexahydridoferrate(II) Salts 160
A. Tetrakis[bromobis(tetrahydrofuran)magnesium] Hexahydridoferrate(II) 161
B. Tetrakis[2-methyl-2-propoxomagnesium] Hexahydridoferrate(II) 163
32. Tris(allyl)iridium and -Rhodium 165
A. Allyllithium 166
B. mer-Trichlorotris(tetrahydrothiophene)iridium(III) 166
C. mer-Trichlorotris(tetrahydrothiophene)rhodium(III) 167
D. Tris(allyl)iridium(III) 168
E. Tris(allyl)rhodium(III) 170
33. Trinuclear Palladium(II) Acetate 171
Chapter Five MAIN GROUP COMPOUNDS AND LIGANDS 174
34. Monocarbaborane Anions with 10 or 12 Vertices 174
A. Tetraethylammonium arachno-6-Carba-decaboranate(14) 176
B. Tetraethylammonium closo-2-Carba-decaboranate(10) 177
C. Tetraethylammonium closo-1-Carba-decaboranate(10) 178
D. Tetraethylammonium closo-1-Carba-dodecaboranate(12) 179
E. Tetraethylammonium nido-6-Phenyl-6-carbadecaboranate(12) 180
F. Tetraethylammonium closo-2-Phenyl-2-carbadecaboranate(10) 181
G. Tetraethylammonium closo-1-Phenyl-1-carbadecaboranate(10) 182
H. Tetraethylammonium closo-1-Phenyl-1-carbadodecaboranate(12) 183
35. Tetrakis(5-tert-butyl-2-hydroxyphenyl)ethene 186
A. 5, 50-Di-tert-butyl-2, 20-dimethoxybenzophenone 187
B. Titanium Trichloride 1, 2-Dimethoxyethane (1:1.5) 189
C. Tetrakis(5-tert-butyl-2-methoxyphenyl)ethene 189
D. Tetrakis(5-tert-butyl-2-hydroxyphenyl)ethene 192
36. Electrochemical Synthesis of Tetraethylammonium Tetrathiooxalate 195
37. Mid-Infrared Emitting Lead Selenide Nanocrystal Quantum Dots 198
A. Lead Selenide NQDs Emitting at 2.5 μm (0.50 e V) 199
B. Lead Selenide NQDs Emitting at 2.8 μm (0.44 e V) 200
C. Lead Selenide NQDs Emitting at 3.3 μm (0.38 e V) 201
D. Lead Selenide NQDs Emitting at 3.5 μm (0.35 e V) 201
Chapter Six TEACHING LABORATORY EXPERIMENTS 203
38. Tetra(acetato)dichromium(II) Dihydrate 203
39. Keggin Structure Polyoxometalates 210
A. Tri(ammonium) 12-Molybdophosphate 211
B. 12-Tungstosilicic Acid 212
C. 12-Tungstophosphoric Acid 214
D. 12-Molybdophosphoric Acid 215
40. Quadruply Metal–Metal Bonded Complexes of Rhenium(III) 217
A. Tetrabutylammonium Perrhenate(VII) 218
B. Bis(tetrabutylammonium) Octachlorodirhenate(III) 219
C. Tetra(acetato)dichlorodirhenium(III) 221
41. Bis[bis(triphenylphosphoranylidene)ammonium] Undecacarbonyltriferrate(2
Despre autor
Professor Gregory S. Girolami received his B.S. degrees in chemistry and physics from the University of Texas at Austin and his Ph.D. degree from the University of California at Berkeley. Thereafter, he was a NATO postdoctoral fellow with Sir Geoffrey Wilkinson at Imperial College of Science and Technology, and joined the Illinois faculty in 1983.
Alfred P. Sattelberger is Argonne’s Associate?Laboratory Director for Energy Engineering and Systems Analysis. He oversees the Energy Engineering and Systems Analysis?Directorate (EESA), which is responsible for Argonne’s programs in energy?research—including energy storage, renewable energy, energy efficiency and nuclear energy—and national security. Sattelberger obtained a Ph.D. in inorganic chemistry from Indiana University and was a National Science Foundation Postdoctoral Fellow at Case Western Reserve University.
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