Inorganic Syntheses, Volume 37

Philip P. Power FRS, is Professor of Inorganic Chemistry at the University of California, Davis, CA.

Note to Contributors and Checkers xv

Toxic Substances and Laboratory Hazards xvii

Preface xix

Chapter One DIVALENT MANGANESE, IRON, AND COBALT BIS(TRIMETHYLSILYL)AMIDO DERIVATIVES AND THEIR TETRAHYDROFURAN COMPLEXES 1

1. Introduction 1

2. Bis{bis(trimethylsilyl)amido}iron(II) dimer: [Fe{N(SiMe3)2}2]2 4

A. Bis{bis(trimethylsilyl)amido}iron(II) dimer: [Fe{N(SiMe3)2}2]2 5

3. Bis{bis(trimethylsilyl)amido}cobalt(II) dimer, [Co{N(SiMe3)2}2]2,and bis{bis(trimethylsilyl)amido}(tetrahydrofuran)cobalt(II),Co{N(SiMe3)2}2(THF) 7

A. Bis{bis(trimethylsilyl)amido}cobalt(II) dimer: [Co{N(SiMe3)2}2]2 . 8

B. Bis{bis(trimethylsilyl)amido}(tetrahydrofuran)cobalt(II): Co{N(SiMe3)2}2(THF) 9

4. Bis{bis(trimethylsilyl)amido}manganese(II) dimer, [Mn{N(SiMe3)2}2]2, and its THF complexes Mn{N(SiMe3)2}2(THF) and Mn{N(SiMe3)2}2(THF)2 10

A. Bis{bis(trimethylsilyl)amido}(tetrahydrofuran)manganese(II),Mn{N(SiMe3)2}2(THF), and bis{bis(trimethylsilyl)amido} manganese(II) dimer, [Mn{N(SiMe3)2}2]2 11

B. Bis{bis(trimethylsilyl)amido}bis(tetrahydrofuran)manganese(II) 12

C. An alternative synthesis of Mn{N(SiMe3)2}2(THF) and [Mn{N(SiMe3)2}2]2 12

Chapter Two CALCIUM, STRONTIUM, GERMANIUM, TIN, AND LEAD BIS(TRIMETHYLSILYL)AMIDO DERIVATIVES AND 2,2,6,6- TETRAMETHYLPIPERIDIDO AND N-ISOPROPYLPHENYLAMIDO DERVATIVES OF POTASSIUM AND CALCIUM 15

1. Introduction 15

2. Potassium (2,2,6,6-tetramethylpiperidide), bis(2,2,6,6- tetramethylpiperidido) (N,N,N’,N’ -tetramethylethylenediamine)calcium(II), potassium (N-isopropylanilido), and bis(N-isopropylanilido) Tris (tetrahydrofuran)calcium(II) 18

A. Potassium 2,2,6,6-tetramethylpiperidide 19

B. Diiodotetrakis(tetrahydrofuran)calcium(II) 20

C. Bis(2,2,6,6-tetramethylpiperidido)(N,N,N’,N’- tetramethylethylenediamine)calcium(II) 20

D. Potassium N-{isopropyl(phenyl)amide} (Potassium N-isopropylanilide) 21

E. Bis{N-isopropyl(phenyl)amido}tris(tetrahydrofuran)calcium(II) 22

F. Bis[{bis(tetrahydrofuran)potassium}bis{μ-N(isopropyl)(phenyl) amido}]calcium(II) 22

3. Bis{bis(trimethylsilyl)amido}calcium(II) dimer, [Ca{N(SiMe3)2}2]2, and bis {bis(trimethylsilyl)amido}strontium(II) dimer, [Sr{N(SiMe3)2}2]2 24

A. Bis{bis(trimethylsilyl)amido}calcium(II) dimer, [Ca{N(SiMe3)2}2]2,and bis{bis(trimethylsilyl)amido}strontium(II) dimer, [Sr{N(SiMe3)2}2]2 25

4. Divalent Group 14 metal bis(trimethylsilylamides), M{N(SiMe3)2}2 (M = Ge, Sn, Pb) 26

A. Bis{bis(trimethylsilyl)amido}germanium(II), Ge{N(SiMe3)2}2 27

B. Bis{bis(trimethylsilyl)amido}tin(II), Sn{N(SiMe3)2}2 28

C. Bis{bis(trimethylsilyl)amido}lead(II), Pb{N(SiMe3)2}2 29

Chapter Three COMPOUNDS WITH Zn–Zn AND Mg–Mg BONDS: DECAMETHYLDIZINCOCENE AND β-DIKETIMINATO COMPLEXES OF MAGNESIUM(I) AND (II) 33

1. Introduction 33

2. Pentamethylcyclopentadienyl zinc(I) dimer, {Zn(η5-C5Me5)}2 37

A. Pentamethylcyclopentadienyl potassium 38

B. Bis(pentamethylcyclopentadienyl)zinc(II) 38

C. Bis(pentamethylcyclopentadienyl)dizinc(I) 39

3. β-diketiminato complexes of magnesium(I)/(II) 40

A. {2,4-bis-(2,6-diisopropylphenylimido)pentyl}(diethylether) iodomagnesium(II), {HC(CMeNC6H3-2,6-Pri 2)2}MgI(OEt2) 41

B. {2,4-bis-(mesitylimido)pentyl}(diethylether) iodidomagnesium(II),{HC(CMeNC6H2-2,4,6-Me3)2}MgI(OEt2) 42

C. Bis{2,4-bis-(2,6-diisopropylphenylimido)pentyl}dimagnesium(I) [{HC(CMeNC6H3-2,6-Pri 2)2}2Mg]2 43

D. Bis{2,4-bis-(mesitylimido)pentyl}dimagnesium(I), [{HC(CMeN(C6H2-2,4,6-Me3)}Mg]2 44

Chapter Four STERICALLY CROWDED σ- AND π-BONDED METAL ARYL COMPLEXES 47

1. Introduction 47

2. Dimesityliron(II) dimer and dimesityldipyridineiron(II) (Mes = Mesityl = C6H2-2,4,6-Me3) 50

A. Tetramesityldiiron(II) dimer (FeMes2)2 (Mes = 2,4,6-trimethylphenyl) 51

B. Dimesityldi(pyridine)iron(II) FeMes2py2 (py = C5H5N) 54

3. Homoleptic, two-coordinate open-shell 2,6-dimesitylphenyl complexes of lithium, manganese, iron, and cobalt 56

A. 1-Iodo-2,6-bis(2,4,6-trimethylphenyl)benzene, 2,6-dimesitylphenyl iodide 57

B. Bis{μ-2,6-bis(2,4,6-trimethylphenyl)phenyl}dilithium, 2,6-dimesitylphenyllithium dimer 58

C. Bis{2,6-bis(2,4,6-trimethylphenyl)phenyl}manganese(II), (bis(2,6-dimesitylphenyl)manganese(II)) 59

D. Bis{2,6-bis(2,4,6-trimethylphenyl)phenyl}iron(II), bis(2,6-dimesitylphenyl)iron(II) 59

E. Bis{2,6-bis(2,4,6-trimethylphenyl)phenyl}cobalt(II),bis(2,6-dimesitylphenyl)cobalt(II) 60

4. Monomeric group 14 diaryls bis{2,6-bis(2,4,6-trimethylphenyl)phenyl} germanium(II), tin(II), or lead(II), M{C6H3-2,6-Mes2)2 and bis{2,6-bis(2,6- diisopropylphenyl)phenyl}germanium(II), tin(II), or lead(II), M{C6H3-2,6-Dipp2}2 (M = Ge, Sn, or Pb; Mes = C6H2-2,4,6-Me3;Dipp = C6H3-2,6-Pri2) 61

5. m-terphenylgallium chloride complexes 65

A. {Bis(diethylether)lithium}{trichlorido(2,6-diphenyl)phenylgallate}, {Li(Et2O)2}{(C6H3-2,6-Ph2)GaCl3} 66

B. Chlorido{bis(2,6-dimesitylphenyl)}gallium, (2,6-Mes2C6H3)2GaCl 67

6. {(18-crown-6)bis(tetrahydrofuran)potassium}{bis(1,2,3,4-η4-anthracene)metallates} of cobalt(-I) and iron(-I),{K(18-crown-6)(THF)2} {M(η4-C14H10)2}, M= Co, Fe 67

A. {(18-crown-6)bis(tetrahydrofuran)potassium}{bis(1,2,3,4-η4-anthracene)cobaltate}, {K(18-crown-6)(THF)2}{Co(C14H10)2} 69

B. {(18-crown-6)bis(tetrahydrofuran)potassium}{bis(1,2,3,4-η4-anthracene)ferrate}, {K(18-crown-6)(THF)2}{Fe(C14H10)2} 70

7. {Bis(1,2-dimethoxyethane)potassium}{bis(1,2,3,4-η4-anthracene) cobaltate}, {K(DME)2}{Co(η4-C14H10)2} 72

8. Cyclopentadienyl and pentamethylcyclopentadienyl naphthalene ferrates 76

A. Bis(tetrahydrofuran)lithium cyclopentadienyl(1,2,3,4-η4-napthalene) ferrate, [{Li(thf)2}{CpFe(η4-C10H8)}] 78

B. (18-crown-6)potassium pentamethylcyclopentadienyl(1,2,3,4-η4- napthalene)ferrate, [K(18-crown-6){Cp∗Fe(η4-C10H8)}] 79

Chapter Five TERPHENYL LIGANDS AND COMPLEXES 85

1. Introduction 85

2. m-Terphenyl iodo and lithium reagents featuring 2,6-bis-(2,6- diisopropylphenyl) substitution patterns and an m-terphenyl lithium etherate featuring the 2,6-bis-(2,4,6-triisopropylphenyl) substitution pattern 89

A. 1-bromo-2,6-diisopropylbenzene, 1-Br-2,6-Pri2C6H3;DippBr) 90

B. 1-iodo-2,6-bis(2,6-diisopropylphenyl)benzene (IC6H3-2,6-Dipp2) 92

C. Bis{2,6-bis(2,6-diisopropylphenyl)phenyl}dilithium,(LiC6H3-2,6-Dipp2)2 94

D. 2,6-bis(2,6-diisopropylphenyl)phenyllithiumetherate 95

E. 2,6-bis(2,4,6-triisopropylphenyl)phenyllithiumetherate{(Et2O)LiC6H3-2,6-Trip2} 96

3. 2,6-dimesitylaniline (H2NC6H3-2,6-Mes2) and 2,6-bis(2,4,6- triisopropylphenyl)aniline (H2NC6H3-2,6-Trip2) 98

A. 2,6-dimesitylphenylazide, 2,6-Mes2C6H3N 99

B. 2,6-dimesitylaniline, 2,6-Mes2C6H3NH2 100

C. 2,6-bis(2,4,6-triisopropylphenyl)iodobenzene, 2,6-Trip2C6H3I 101

D. 2,6-bis(2,4,6-triisopropylphenyl)azidobenzene,2,6-Trip2C6H3N3 102

E. 2,6-bis(2,4,6-triisopropylphenyl)aniline, 2,6-Trip2C6H3NH2 103

4. Bis-2,6-(2,6-diisopropylphenyl)aniline 105

A. 1-azido-bis-2,6-(2,6-diisopropylphenyl)benzene,2,6-Dipp2H3C6N3 106

B. Bis-2,6-(2,6-diisopropylphenyl)aniline, 2,6-Dipp2H3C6NH2 107

5. Bis-2,6-(2,4,6-trimethylphenyl)phenylformamide and isocyanide,Bis-2,6-(2,6-diisopropylphenyl)phenylformamide and isocyanide 109

A. 2,6-dimesitylphenyl formamide {2,6-Mes2H3C6N(H)C(O)H} 110

B. 2,6-dimesitylphenyl isocyanide (2,6-Mes2H3C6NC) 111

C. 2,6-bis-(diisopropylphenyl)phenyl formamide{2,6-Dipp2H3C6N(H)C(O)H} 112

D. 2,6-bis-(diisopropylphenyl)phenyl isocyanide (2,6-Dipp2H3C6NC) 113

6. Synthesis of the terphenylthiols: 2,6-bis(2,6-diisopropylphenyl)phenylthiol,2,6-bis(2,4,6-triisopropylphenyl)phenylthiol, and bis{2,6-bis(2,4,6-triisopropylphenyl)phenylthiolato}dilithium 116

A. 2,6-bis(2,6-diisopropylphenyl)phenylthiol 117

B. 2,6-bis(2,4,6-triisopropylphenyl)phenylthiol 118

C. Bis{2,6-bis(2,4,6-triisopropylphenyl)phenylthiolato}dilithium 119

7. Sterically encumbered terphenols: 2,6-bis(2,4,6-trimethylphenyl)phenol and 2,6-bis(2,6-diisopropylphenyl)phenol 120

A. 2,6-bis(2,6-diisopropylphenyl)phenol 121

B. Bis(2,4,6-trimethylphenyl)phenol 121

Chapter Six SYNTHETIC ROUTES TO WHITE PHOSPHORUS (P4) AND ARSENIC TRIPHOSPHIDE (AsP3) 123

1. Introduction 123

2. Facile preparation of white phosphorus from red phosphorus:Preparation A 125

3. Synthesis of white phosphorus (P4) from red phosphorus:Preparation B 127

4. Arsenic triphosphide, AsP3 130

A. Tris(2,6-diisopropylphenoxy)niobiumdichloride {Cl2Nb(ODipp)3} and Tris(2,6-diisopropylphenoxy)niobiumdichloride(tetrahydrofuran) {Cl2Nb(ODipp)3(THF)} 131

B. {Na(THF)3}{P3Nb(ODipp)3} 132

C. Arsenic Triphosphide AsP3 133

Chapter Seven SYNTHETIC ROUTES TO PHOSPHIDO AND ARSENIDO DERIVATIVES OF THE GROUP 13 METALS ALUMINUM, GALLIUM, AND INDIUM, TRIS(TERT-BUTYL)GALLIUM AND ITS REACTIONS WITH AMMONIA, AND THE ALUMINUM(I) SPECIES PENTAMETHYLCYCLOPENTADIENYL ALUMINUM TETRAMER 135

1. Introduction 135

2. Dinuclear phosphido and arsenido derivatives of aluminum, gallium, and indium {Me2M(μ-EBut2)}2, M= Al, Ga, In; E = P, As 137

A. Preparation of {Me2M(μ-EBut2)}2 Complexes: M= Al,Ga, In; E = P, As 138

3. Tris(tert-butyl)gallane, its ammonia complex, and the amidobis(tert-butyl)gallane trimer tris(μ-amido)hexa(tert-butyl)trigallium 140

A. Tri-tert-butylgallane 141

B. Ammonia complex of tri-tert-butylgallane 142

C. Tris(μ-amido)hexa-tert-butyltrigallium: The trimer {But2Ga (μ-NH2)}3 143

4. Reductive elimination as a convenient pathway to tetrameric (η5-pentamethylcyclopentadienyl)aluminum(I) {(AlCp∗)4} (Cp∗ = η5-C5Me5) 144

A. Potassium pentamethylcyclopentadienide KCp∗ 146

B. Bis(pentamethylcyclopentadienyl)aluminumhydride (Cp∗2AlH) 146

C. Tetrameric (η5-pentamethylcyclopentadienyl)aluminum(I){(AlCp∗)4} 147

5. A facile synthesis of tetrameric (ƞ5-pentamethylycycloclopentadienyl) aluminum(I) {Al(ƞ5-C5Me5)}4 147

A. (ƞ5-pentamethylcyclopentadienyl)aluminumdichloride 149

B. Tetrameric (ƞ5-pentamethylcyclopentadienyl)aluminum(I) (AlCp∗)4 149

6. Tris(pentafluorophenyl)aluminum(toluene): Al(C6F5)3(C7H8) 150

A. Tris(pentafluorophenyl)aluminum(toluene) 151

Chapter Eight SYNTHESIS OF SELECTED TRANSITION METAL AND MAIN GROUP COMPOUNDS WITH SYNTHETIC APPLICATIONS 155

1. Introduction 155

2. Synthesis of gold(I) and gold(II) amidinate complexes 157

A. Synthesis of gold(I) amidinate complexes 158

B. Synthesis of gold(II) amidinate complexes 161

3. A nickel–iron thiolate and its hydride 166

A. (1,2-bis(diphenylphosphino)ethane)(1,3-propanedithiolato) nickel(II) 167

B. (1,2-bis(diphenylphosphino)ethane)nickel(I)(μ-1,3- propanedithiolato)tricarbonyliron(I)  168

C. (1,2-bis(diphenylphosphino)ethane)nickel(II)(μ-hydrido)(μ-1,3-propanedithiolato)tricarbonyliron(II) tetrafluoroborate 169

4. Dimethyl sulfoxide and organophosphine complexes of ruthenium(II) halides 171

A. cis-tetrakis(dimethylsulfoxide)ruthenium(II)dichloride 172

B. cis-bis{1,2-bis(diphenylphosphino)ethane}ruthenium(II) dichloride 174

C. Bis{1,2-bis(diphenylphosphino)ethane}chlororuthenium(II) hexafluorophosphate 174

D. trans-bis{1,2-bis(diphenylphosphino)ethane}ruthenium(II) dichloride 176

5. Synthesis of {CrIII(NCMe)6}(BF4)3 and {CrIII(NCMe)5F} (BF4)2•MeCN 177

A. Hexakis(acetonitrile)chromium(III) tetrafluoroborate, {CrIII(NCMe)6}(BF4)3 177

B. Pentakis(acetonitrile)fluorido chromium(III) tetrafluoroborate, {CrIIIF(NCMe)5}(BF4)2 178

6. (1R,2R-diaminocyclohexane)oxalatoplatinum(II), oxaliplatin 179

7. Tris(dibenzylideneacetone)dipalladium(0) 183

A. Synthesis of Pd2dba3·CHCl3 185

B. Purity determination and repurification of Pd2dba3 186

C. Stability 187

8. Tetraalkylammonium salts of tetra(fluoroaryl)borate anions 188

A. Tetraalkylammonium salts of [B(C6F5)4]− 189

B. Tetraalkylammonium salts of [B{C6H3-3,5-(CF3)2}4]− 191

9. Titanium tris(N-tert-butyl, 3,5-dimethylanilide) 193

10. Tetrachlorido(tetramethylethylenediamine)tantalum(IV),TaCl4(TMEDA) 196

A. Tetrachlorido(tetramethylethyenediamine)tantalum(IV),TaCl4(TMEDA) 197

11. Synthesis of 1,3,5-tri-tert-butylcyclopenta-1,3-diene and its metal complexes Na{1,2,4-(Me3C)3C5H2} and Mg{η5-1,2,4-(Me3C)3C5H2}2 199

A. Method A (Phase Transfer) 199

B. Method B (Grignard Procedure) 201

C. Sodium(1,2,4-tri-tert-butyl)cyclopentadienide 203

D. Magnesium(II)bis(1,2,4-tri-tert-butyl)cyclopentadienide 203

Cumulative Contributor Index 205

Cumulative Subject Index 215

Cumulative Formula Index 245