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

• Note to Contributors and Checkers xvToxic Substances and Laboratory Hazards xviiPreface xixChapter One DIVALENT MANGANESE, IRON, AND COBALT BIS(TRIMETHYLSILYL)AMIDO DERIVATIVES AND THEIR TETRAHYDROFURAN COMPLEXES 11. Introduction 12. Bis{bis(trimethylsilyl)amido}iron(II) dimer: [Fe{N(SiMe3)2}2]2 4A. Bis{bis(trimethylsilyl)amido}iron(II) dimer: [Fe{N(SiMe3)2}2]2 53. 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) 7A. Bis{bis(trimethylsilyl)amido}cobalt(II) dimer: [Co{N(SiMe3)2}2]2 . 8B. Bis{bis(trimethylsilyl)amido}(tetrahydrofuran)cobalt(II): Co{N(SiMe3)2}2(THF) 94. 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 10A. 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 11B. Bis{bis(trimethylsilyl)amido}bis(tetrahydrofuran)manganese(II) 12C. An alternative synthesis of Mn{N(SiMe3)2}2(THF) and [Mn{N(SiMe3)2}2]2 12Chapter 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 151. Introduction 152. 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) 18A. Potassium 2,2,6,6-tetramethylpiperidide 19B. Diiodotetrakis(tetrahydrofuran)calcium(II) 20C. Bis(2,2,6,6-tetramethylpiperidido)(N,N,N’,N’- tetramethylethylenediamine)calcium(II) 20D. Potassium N-{isopropyl(phenyl)amide} (Potassium N-isopropylanilide) 21E. Bis{ N-isopropyl(phenyl)amido}tris(tetrahydrofuran)calcium(II) 22F. Bis[{bis(tetrahydrofuran)potassium}bis{μ-N(isopropyl)(phenyl) amido}]calcium(II) 223. 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 24A. 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]2 254. Divalent Group 14 metal bis(trimethylsilylamides), M{N(SiMe3)2}2 (M = Ge, Sn, Pb) 26A. Bis{bis(trimethylsilyl)amido}germanium(II), Ge{N(SiMe3)2}2 27B. Bis{bis(trimethylsilyl)amido}tin(II), Sn{N(SiMe3)2}2 28C. Bis{bis(trimethylsilyl)amido}lead(II), Pb{N(SiMe3)2}2 29Chapter Three COMPOUNDS WITH Zn–Zn AND Mg–Mg BONDS: DECAMETHYLDIZINCOCENE AND β-DIKETIMINATO COMPLEXES OF MAGNESIUM(I) AND (II) 331. Introduction 332. Pentamethylcyclopentadienyl zinc(I) dimer, {Zn(η5-C5Me5)}2 37A. Pentamethylcyclopentadienyl potassium 38B. Bis(pentamethylcyclopentadienyl)zinc(II) 38C. Bis(pentamethylcyclopentadienyl)dizinc(I) 393. β-diketiminato complexes of magnesium(I)/(II) 40A. {2,4-bis-(2,6-diisopropylphenylimido)pentyl}(diethylether) iodomagnesium(II), {HC(CMeNC6H3-2,6-Pri 2)2}MgI(OEt2) 41B. {2,4-bis-(mesitylimido)pentyl}(diethylether) iodidomagnesium(II),{HC(CMeNC6H2-2,4,6-Me3)2}MgI(OEt2) 42C. Bis{2,4-bis-(2,6-diisopropylphenylimido)pentyl}dimagnesium(I) [{HC(CMeNC6H3-2,6-Pri 2)2}2Mg]2 43D. Bis{2,4-bis-(mesitylimido)pentyl}dimagnesium(I), [{HC(CMeN(C6H2-2,4,6-Me3)}Mg]2 44Chapter Four STERICALLY CROWDED σ- AND π-BONDED METAL ARYL COMPLEXES 471. Introduction 472. Dimesityliron(II) dimer and dimesityldipyridineiron(II) (Mes = Mesityl = C6H2-2,4,6-Me3) 50A. Tetramesityldiiron(II) dimer (FeMes2)2 (Mes = 2,4,6-trimethylphenyl) 51B. Dimesityldi(pyridine)iron(II) FeMes2py2 (py = C5H5N) 543. Homoleptic, two-coordinate open-shell 2,6-dimesitylphenyl complexes of lithium, manganese, iron, and cobalt 56A. 1-Iodo-2,6-bis(2,4,6-trimethylphenyl)benzene, 2,6-dimesitylphenyl iodide 57B. Bis{μ-2,6-bis(2,4,6-trimethylphenyl)phenyl}dilithium, 2,6-dimesitylphenyllithium dimer 58C. Bis{2,6-bis(2,4,6-trimethylphenyl)phenyl}manganese(II), (bis(2,6-dimesitylphenyl)manganese(II)) 59D. Bis{2,6-bis(2,4,6-trimethylphenyl)phenyl}iron(II), bis(2,6-dimesitylphenyl)iron(II) 59E. Bis{2,6-bis(2,4,6-trimethylphenyl)phenyl}cobalt(II),bis(2,6-dimesitylphenyl)cobalt(II) 604. 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) 615. m-terphenylgallium chloride complexes 65A. {Bis(diethylether)lithium}{trichlorido(2,6-diphenyl)phenylgallate}, {Li(Et2O)2}{(C6H3-2,6-Ph2)GaCl3} 66B. 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 67A. {(18-crown-6)bis(tetrahydrofuran)potassium}{bis(1,2,3,4-η4-anthracene)cobaltate}, {K(18-crown-6)(THF)2}{Co(C14H10)2} 69B. {(18-crown-6)bis(tetrahydrofuran)potassium}{bis(1,2,3,4-η4-anthracene)ferrate}, {K(18-crown-6)(THF)2}{Fe(C14H10)2} 707. {Bis(1,2-dimethoxyethane)potassium}{bis(1,2,3,4-η4-anthracene) cobaltate}, {K(DME)2}{Co(η4-C14H10)2} 728. Cyclopentadienyl and pentamethylcyclopentadienyl naphthalene ferrates 76A. Bis(tetrahydrofuran)lithium cyclopentadienyl(1,2,3,4-η4-napthalene) ferrate, [{Li(thf)2}{CpFe(η4-C10H8)}] 78B. (18-crown-6)potassium pentamethylcyclopentadienyl(1,2,3,4-η4- napthalene)ferrate, [K(18-crown-6){Cp∗Fe(η4-C10H8)}] 79Chapter Five TERPHENYL LIGANDS AND COMPLEXES 851. Introduction 852. 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 89A. 1-bromo-2,6-diisopropylbenzene, 1-Br-2,6-Pri2C6H3;DippBr) 90B. 1-iodo-2,6-bis(2,6-diisopropylphenyl)benzene (IC6H3-2,6-Dipp2) 92C. Bis{2,6-bis(2,6-diisopropylphenyl)phenyl}dilithium,(LiC6H3-2,6-Dipp2)2 94D. 2,6-bis(2,6-diisopropylphenyl)phenyllithiumetherate 95E. 2,6-bis(2,4,6-triisopropylphenyl)phenyllithiumetherate{(Et2O)LiC6H3-2,6-Trip2} 963. 2,6-dimesitylaniline (H2NC6H3-2,6-Mes2) and 2,6-bis(2,4,6- triisopropylphenyl)aniline (H2NC6H3-2,6-Trip2) 98A. 2,6-dimesitylphenylazide, 2,6-Mes2C6H3N 99B. 2,6-dimesitylaniline, 2,6-Mes2C6H3NH2 100C. 2,6-bis(2,4,6-triisopropylphenyl)iodobenzene, 2,6-Trip2C6H3I 101D. 2,6-bis(2,4,6-triisopropylphenyl)azidobenzene,2,6-Trip2C6H3N3 102E. 2,6-bis(2,4,6-triisopropylphenyl)aniline, 2,6-Trip2C6H3NH2 1034. Bis-2,6-(2,6-diisopropylphenyl)aniline 105A. 1-azido-bis-2,6-(2,6-diisopropylphenyl)benzene,2,6-Dipp2H3C6N3 106B. Bis-2,6-(2,6-diisopropylphenyl)aniline, 2,6-Dipp2H3C6NH2 1075. Bis-2,6-(2,4,6-trimethylphenyl)phenylformamide and isocyanide,Bis-2,6-(2,6-diisopropylphenyl)phenylformamide and isocyanide 109A. 2,6-dimesitylphenyl formamide {2,6-Mes2H3C6N(H)C(O)H} 110B. 2,6-dimesitylphenyl isocyanide (2,6-Mes2H3C6NC) 111C. 2,6-bis-(diisopropylphenyl)phenyl formamide{2,6-Dipp2H3C6N(H)C(O)H} 112D. 2,6-bis-(diisopropylphenyl)phenyl isocyanide (2,6-Dipp2H3C6NC) 1136. 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 116A. 2,6-bis(2,6-diisopropylphenyl)phenylthiol 117B. 2,6-bis(2,4,6-triisopropylphenyl)phenylthiol 118C. Bis{2,6-bis(2,4,6-triisopropylphenyl)phenylthiolato}dilithium 1197. Sterically encumbered terphenols: 2,6-bis(2,4,6-trimethylphenyl)phenol and 2,6-bis(2,6-diisopropylphenyl)phenol 120A. 2,6-bis(2,6-diisopropylphenyl)phenol 121B. Bis(2,4,6-trimethylphenyl)phenol 121Chapter Six SYNTHETIC ROUTES TO WHITE PHOSPHORUS (P4) AND ARSENIC TRIPHOSPHIDE (AsP3) 1231. Introduction 1232. Facile preparation of white phosphorus from red phosphorus:Preparation A 1253. Synthesis of white phosphorus (P4) from red phosphorus:Preparation B 1274. Arsenic triphosphide, AsP3 130A. Tris(2,6-diisopropylphenoxy)niobiumdichloride {Cl2Nb(ODipp)3} and Tris(2,6-diisopropylphenoxy)niobiumdichloride(tetrahydrofuran) {Cl2Nb(ODipp)3(THF)} 131B. {Na(THF)3}{P3Nb(ODipp)3} 132C. Arsenic Triphosphide AsP3 133Chapter 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 1351. Introduction 1352. Dinuclear phosphido and arsenido derivatives of aluminum, gallium, and indium {Me2M(μ-EBut2)}2, M= Al, Ga, In; E = P, As 137A. Preparation of {Me2M(μ-EBut2)}2 Complexes: M= Al,Ga, In; E = P, As 1383. Tris(tert-butyl)gallane, its ammonia complex, and the amidobis(tert-butyl)gallane trimer tris(μ-amido)hexa(tert-butyl)trigallium 140A. Tri-tert-butylgallane 141B. Ammonia complex of tri-tert-butylgallane 142C. Tris(μ-amido)hexa-tert-butyltrigallium: The trimer {But2Ga (μ-NH2)}3 1434. Reductive elimination as a convenient pathway to tetrameric (η5-pentamethylcyclopentadienyl)aluminum(I) {(AlCp∗)4} (Cp∗ = η5-C5Me5) 144A. Potassium pentamethylcyclopentadienide KCp∗ 146B. Bis(pentamethylcyclopentadienyl)aluminumhydride (Cp∗2AlH) 146C. Tetrameric (η5-pentamethylcyclopentadienyl)aluminum(I){(AlCp∗)4} 1475. A facile synthesis of tetrameric (ƞ5-pentamethylycycloclopentadienyl) aluminum(I) {Al(ƞ5-C5Me5)}4 147A. (ƞ5-pentamethylcyclopentadienyl)aluminumdichloride 149B. Tetrameric (ƞ5-pentamethylcyclopentadienyl)aluminum(I) (AlCp∗)4 1496. Tris(pentafluorophenyl)aluminum(toluene): Al(C6F5)3(C7H8) 150A. Tris(pentafluorophenyl)aluminum(toluene) 151Chapter Eight SYNTHESIS OF SELECTED TRANSITION METAL AND MAIN GROUP COMPOUNDS WITH SYNTHETIC APPLICATIONS 1551. Introduction 1552. Synthesis of gold(I) and gold(II) amidinate complexes 157A. Synthesis of gold(I) amidinate complexes 158B. Synthesis of gold(II) amidinate complexes 1613. A nickel–iron thiolate and its hydride 166A. (1,2-bis(diphenylphosphino)ethane)(1,3-propanedithiolato) nickel(II) 167B. (1,2-bis(diphenylphosphino)ethane)nickel(I)(μ-1,3- propanedithiolato)tricarbonyliron(I)  168C. (1,2-bis(diphenylphosphino)ethane)nickel(II)(μ-hydrido)(μ-1,3-propanedithiolato)tricarbonyliron(II) tetrafluoroborate 1694. Dimethyl sulfoxide and organophosphine complexes of ruthenium(II) halides 171A. cis-tetrakis(dimethylsulfoxide)ruthenium(II)dichloride 172B. cis-bis{1,2-bis(diphenylphosphino)ethane}ruthenium(II) dichloride 174C. Bis{1,2-bis(diphenylphosphino)ethane}chlororuthenium(II) hexafluorophosphate 174D. trans-bis{1,2-bis(diphenylphosphino)ethane}ruthenium(II) dichloride 1765. Synthesis of {CrIII(NCMe)6}(BF4)3 and {CrIII(NCMe)5F} (BF4)2•MeCN 177A. Hexakis(acetonitrile)chromium(III) tetrafluoroborate, {CrIII(NCMe)6}(BF4)3 177B. Pentakis(acetonitrile)fluorido chromium(III) tetrafluoroborate, {CrIIIF(NCMe)5}(BF4)2 1786. (1R,2R-diaminocyclohexane)oxalatoplatinum(II), oxaliplatin 1797. Tris(dibenzylideneacetone)dipalladium(0) 183A. Synthesis of Pd2dba3·CHCl3 185B. Purity determination and repurification of Pd2dba3 186C. Stability 1878. Tetraalkylammonium salts of tetra(fluoroaryl)borate anions 188A. Tetraalkylammonium salts of [B(C6F5)4]− 189B. Tetraalkylammonium salts of [B{C6H3-3,5-(CF3)2}4]− 1919. Titanium tris(N-tert-butyl, 3,5-dimethylanilide) 19310. Tetrachlorido(tetramethylethylenediamine)tantalum(IV),TaCl4(TMEDA) 196A. Tetrachlorido(tetramethylethyenediamine)tantalum(IV),TaCl4(TMEDA) 19711. 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 199A. Method A (Phase Transfer) 199B. Method B (Grignard Procedure) 201C. Sodium(1,2,4-tri-tert-butyl)cyclopentadienide 203D. Magnesium(II)bis(1,2,4-tri-tert-butyl)cyclopentadienide 203Cumulative Contributor Index 205Cumulative Subject Index 215Cumulative Formula Index 245