Inorganic Syntheses, Volume 36 Inorganic Syntheses Series

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, MoCl₃(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.

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 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

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.