Inorganic Syntheses, Volume 36

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(¿5-pentamethylcyclopentadienyl) Complexes of Scandium 42

A. Bis(¿5-pentamethylcyclopentadienyl)chloroscandium 43

B. Bis(¿5-pentamethylcyclopentadienyl)methylscandium 44

C. Bis(¿5-pentamethylcyclopentadienyl)phenylscandium 45

D. Bis(¿5-pentamethylcyclopentadienyl)(o-tolyl)scandium 46

10. Bis(¿5-pentamethylcyclopentadienyl) Complexes of Titanium, Zirconium, and Hafnium 47

A. Bis(¿5-pentamethylcyclopentadienyl)dichlorotitanium(IV) 47

B. Bis(¿5-pentamethylcyclopentadienyl)dichlorozirconium(IV) 49

C. Bis(¿5-pentamethylcyclopentadienyl)dichlorohafnium(IV)50

11. Bis(¿5-pentamethylcyclopentadienyl) Complexes of Niobium and Tantalum 52

A. Bis(¿5-pentamethylcyclopentadienyl)dichlorotantalum(IV) 53

B. Bis(¿5-pentamethylcyclopentadienyl)dichloroniobium(IV) 55

12. Bis(¿5-pentamethylcyclopentadienyl) Complexes of Molybdenum 58

A. Bis(pentamethylcyclopentadienyl)dichloromolybdenum(IV) 59

B. Bis(pentamethylcyclopentadienyl)dihydridomolybdenum(IV) 61

13. (¿5-Cyclopentadienyl)tricarbonylmanganese(I) Complexes 62

A. (¿5-Cyclopentadienyl)tricarbonylmanganese(I) 63

B. (¿5-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(¿5-pentamethylcyclopentadienyl) Complexes of Osmium 72

A. Bromoosmic Acid 74

B. Bis(¿5-pentamethylcyclopentadienyl)tetrabromodiosmium(III) 75

C. (¿5-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-¿2,¿2-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 eV) 199

B. Lead Selenide NQDs Emitting at 2.8 µm (0.44 eV) 200

C. Lead Selenide NQDs Emitting at 3.3 µm (0.38 eV) 201

D. Lead Selenide NQDs Emitting at 3.5 µm (0.35 eV) 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