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Inorganic Syntheses, Volume 37

Inorganic Syntheses, Volume 37

Philip P. Power (Editor)

ISBN: 978-1-119-47782-2

Jul 2018

288 pages

Description

The newest volume in the authoritative Inorganic Syntheses book series provides users of inorganic substances with detailed and foolproof procedures for the preparation of important and timely inorganic and organometallic compounds that can be used in reactions to develop new materials, drug targets, and bio-inspired chemical entities.

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. Diiodo tetrakis(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-Pri 2) 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-Pri 2C6H3; 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-Mes2C6H3N3   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-EBut 2)}2, M= Al, Ga, In; E = P, As   137

A. Preparation of {Me2M(μ-EBut 2)}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 {But 2Ga (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)(m-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

Index    205