Inorganic Syntheses, Volume 36

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.

• Preface v Dedication viiNotice to Contributors and Checkers xvToxic Substances and Laboratory Hazards xviiChapter One TRANSITION METAL HALIDE COMPOUNDS 11. Octahedral Hexatantalum Halide Clusters 1A. Tetradecachlorohexatantalum Octahydrate 3B. Tetradecabromohexatantalum Octahydrate 4C. Tetrakis(benzyltributylammonium) Octadecachlorohexatantalate  52. Octahedral Hexamolybdenum Halide Clusters  8A. Tetradecachlorohexamolybdate Hexahydrate (Chloromolybdic Acid) 10B. Hexamolybdenum Dodecachloride  123. Ether Complexes of Molybdenum(III) and Molybdenum(IV) Chlorides 15A. Tetrachlorobis(diethyl ether)molybdenum(IV)  16B. Trichlorotris(tetrahydrofuran)molybdenum(III) 174. Octahedral Hexatungsten Halide Clusters 19A. Bis(hydroxonium) Tetradecachlorohexatungstate Heptahydrate (Chlorotungstic Acid) 21B. Hexatungsten Dodecachloride 225. Trinuclear Tungsten Halide Clusters   24A. Tritungsten Decachloride   26B. Trisodium Tridecachlorotritungstate 27C. Tris(benzyltributylammonium) Tridecachlorotritungstate 286. Crystalline and Amorphous Forms of Tungsten Tetrachloride 30A. Crystalline Tungsten Tetrachloride by Solid-State Reduction   32B. Amorphous Tungsten Tetrachloride by Solution-Phase Reduction 33Chapter Two CYCLOPENTADIENYL COMPOUNDS 357. Sodium and Potassium Cyclopentadienide 35A. Sodium Cyclopentadienide 36B. Potassium Cyclopentadienide 378. (Pentafluorophenyl)cyclopentadiene and its Sodium Salt 38A. (Pentafluorophenyl)cyclopentadiene 39B. Sodium (Pentafluorophenyl)cyclopentadienide  419. Bis(η5-pentamethylcyclopentadienyl) Complexes of Scandium 42A. Bis(η5-pentamethylcyclopentadienyl)chloroscandium 43B. Bis(η5-pentamethylcyclopentadienyl)methylscandium 44C. Bis(η5-pentamethylcyclopentadienyl)phenylscandium 45D. Bis(η5-pentamethylcyclopentadienyl)(o-tolyl)scandium  4610. Bis(η5-pentamethylcyclopentadienyl) Complexes of Titanium, Zirconium, and Hafnium 47A. Bis(η5-pentamethylcyclopentadienyl)dichlorotitanium(IV) 47B. Bis(η5-pentamethylcyclopentadienyl)dichlorozirconium(IV) 49C. Bis(η5-pentamethylcyclopentadienyl)dichlorohafnium(IV)5011. Bis(η5-pentamethylcyclopentadienyl) Complexes of Niobium and Tantalum 52A. Bis(η5-pentamethylcyclopentadienyl)dichlorotantalum(IV) 53B. Bis(η5-pentamethylcyclopentadienyl)dichloroniobium(IV) 5512. Bis(η5-pentamethylcyclopentadienyl) Complexes of Molybdenum 58A. Bis(pentamethylcyclopentadienyl)dichloromolybdenum(IV) 59B. Bis(pentamethylcyclopentadienyl)dihydridomolybdenum(IV) 6113. (η5-Cyclopentadienyl)tricarbonylmanganese(I) Complexes 62A. (η5-Cyclopentadienyl)tricarbonylmanganese(I) 63B. (η5-Pentamethylcyclopentadienyl)tricarbonylmanganese(I) 6314. 1,10-Diaminoferrocene 65A. 1,10-Dilithioferrocene N,N,N0,N0-Tetramethylethylenediamine 66B. 1,10-Dibromoferrocene 67C. One-Pot Preparation of 1,10-Dibromoferrocene from Ferrocene  68D. 1,10-Diaminoferrocene 69E. 1,10-Diaminoferrocenium Hexafluorophosphate 70F. 1,10-Diaminoferrocenium Triflate  7115. Mono(η5-pentamethylcyclopentadienyl) Complexes of Osmium 72A. Bromoosmic Acid 74B. Bis(η5-pentamethylcyclopentadienyl)tetrabromodiosmium(III) 75C. (η5-Pentamethylcyclopentadienyl)(1,5-cyclooctadiene)-bromoosmium(II) 76Chapter Three COMPOUNDS WITH METAL–METAL BONDS 7816. Tetra(acetato)dimolybdenum(II)  7817. Supramolecular Arrays Based on Dimolybdenum Building Blocks 81A. Tetrakis(N,N0-di-p-anisylformamidinato)dimolybdenum(II) 84B. Tris(N,N0-di-p-anisylformamidinato)di(chloro)-dimolybdenum(II,III) 86C. cis-Bis(N,N0-di-p-anisylformamidinato)tetrakis(acetonitrile)-dimolybdenum(II) Bis(tetrafluoroborate)  87D. (μ2-Succinato)bis[tris(N,N0-di-p-anisylformamidinato)-dimolybdenum(II)] 88E. (μ2-η2,η2-Molybdato)bis[tris(N,N0-di-p-anisylformamidinato)-dimolybdenum(II)] 89F. (μ2-N,N0-Diphenylterephthaloyldiamidato)bis[tris(N,N0-di-panisylformamidinato) dimolybdenum(II)]  90G. Molecular Propeller: (μ3-Trimesate)tris[tris(N,N0-di-panisylformamidinato) dimolybdenum(II)]  91H. Molecular Loop: closo-Bis(μ2-malonato)bis[bis(N,N0-di-panisylformamidinato) dimolybdenum(II)]  92I. Molecular Triangle: closo-Tris(μ2-eq,eq-1,4-cyclohexanedicarboxylato) tris[bis(N,N0-di-p-anisylformamidinato)-dimolybdenum(II)]92J. Molecular Square: closo-Tetrakis(μ2-oxalato)tetrakis[bis(N,N0-di-p-anisylformamidinato)dimolybdenum(II)]  93K. Molecular Cage: closo-Tetrakis(μ3-trimesate)hexakis[bis(N,N0-di-p-anisylformamidinato)dimolybdenum(II)]  9418. Dimolybdenum and Ditungsten Hexa(alkoxides) 95A. Hexa(tert-butoxy)dimolybdenum(III) 96B. Hexakis(2-trifluoromethyl-2-propoxy)dimolybdenum(III) 97C. Sodium Heptachloropentakis(tetrahydrofuran)ditungstate(III)   98D. Hexa(tert-butoxy)ditungsten(III) 99E. Hexakis(2-trifluoromethyl-2-propoxy)ditungsten(III)  10019. Linear Trichromium, Tricobalt, Trinickel, and Tricopper Complexes of 2,20-Dipyridylamide 102A. Dichlorotetrakis(2,20-dipyridylamido)trichromium(II) 103B. Dichlorotetrakis(2,20-dipyridylamido)tricobalt(II) 104C. Dichlorotetrakis(2,20-dipyridylamido)trinickel(II) 105D. Dichlorotetrakis(2,20-dipyridylamido)tricopper(II) 106E. Bis(acetonitrile)tetrakis(2,20-dipyridylamido)trichromium(II) Bis(hexafluorophosphate)  107F. Bis(acetonitrile)tetrakis(2,20-dipyridylamido)tricobalt(II) Bis(hexafluorophosphate)  108G. Bis(acetonitrile)tetrakis(2,20-dipyridylamido)trinickel(II) Bis(hexafluorophosphate)  10820. Bis(tetrabutylammonium) Octachloroditechnetate(III) 110A. Tetrabutylammonium Pertechnetate(VII) 111B. Tetrabutylammonium Oxotetrachlorotechnetate(V) 112C. Bis(tetrabutylammonium) Octachloroditechnetate(III) 11221. Diruthenium Formamidinato Complexes 114A. Chlorotris(acetato)(N,N0-di-2,6-xylylformamidinato)-diruthenium(II,III) 115B. trans-Chlorobis(acetato)bis(N,N0-di-2,6-xylylformamidinato)-diruthenium(II,III) 117C. cis-Chlorobis(acetato)bis(N,N0-di-p-anisylformamidinato)-diruthenium(II,III) 118D. Chloro(acetato)tris(N,N0-di-p-anisylformamidinato)-diruthenium(II,III) 119E. Chlorotetrakis(N,N0-di-p-anisylformamidinato)-diruthenium(II,III) 12022. Heptacarbonyl(disulfido)dimanganese(I)  12223. Di(carbido)tetracosa(carbonyl)decaruthenate(2–) Salts 124A. Calcium Di(carbido)tetracosa(carbonyl)decaruthenate(2–) 124B. Bis[bis(triphenylphosphoranylidene)ammonium] Di(carbido)tetracosa(carbonyl)decaruthenate(2–) 125Chapter Four GENERAL TRANSITION METAL COMPOUNDS 12724. Bis(1,2-bis(dimethylphosphano)ethane)tricarbonyltitanium(0) and Hexacarbonyltitanate(2–) 127A. Bis(1,2-bis(dimethylphosphano)ethane)-tricarbonyltitanium(0) 129B. Bis[18-crown-6)(acetonitrile)potassium] Hexacarbonyltitanate(2–)  13125. Tungsten Benzylidyne Complexes 134A. Trichloro(1,2-dimethoxyethane)benzylidynetungsten(VI) 135B. Chloro Bis[1,2-bis(diphenylphosphino)ethane]-benzylidynetungsten(IV)  13626. Tungsten Oxytetrachloride and (Acetonitrile)tetrachlorotungsten Imido Complexes 138A. Tungsten Oxytetrachloride 139B. (Acetonitrile)tetrachloro(phenylimido)tungsten(VI) 140C. (Acetonitrile)tetrachloro(2-propylimido)tungsten(VI)  141D. (Acetonitrile)tetrachloro(2-propenylimido)tungsten(VI) 14227. Tungsten Oxytetrachloride and Several Tungstate Salts 143A. Tungsten Oxytetrachloride 144B. Bis(tetrabutylammonium) Hexapolytungstate 145C. Di(cetylpyridinium) Peroxoditungstate  146D. Bis(tetrabutylammonium) Phenylphosphonatodiperoxotungstate  14728. Bromotricarbonyldi(pyridine)manganese(I)  14829. Bis(tetraethylammonium) fac-Tribromotricarbonylrhenate(I) and -Technetate(I) 149A. Bis(tetraethylammonium) fac-Tribromotricarbonylrhenate(I)  151B. Bis(tetraethylammonium) fac-Trichlorotricarbonyltechnetate(I) 15230. Methyl(oxo)rhenium(V) Complexes with Chelating Ligands 155A. Methyl(oxo)(1,2-ethanedithiolato)rhenium(V) Dimer  156B. Methyl(oxo)bis(2-oxyquinoline)rhenium(V)  157C. Methyl(oxo)(2,20-thiodiacetato)(triphenylphosphine)-rhenium(V) 15831. Hexahydridoferrate(II) Salts   160A. Tetrakis[bromobis(tetrahydrofuran)magnesium] Hexahydridoferrate(II) 161B. Tetrakis[2-methyl-2-propoxomagnesium] Hexahydridoferrate(II) 16332. Tris(allyl)iridium and -Rhodium 165A. Allyllithium 166B. mer-Trichlorotris(tetrahydrothiophene)iridium(III) 166C. mer-Trichlorotris(tetrahydrothiophene)rhodium(III) 167D. Tris(allyl)iridium(III) 168E. Tris(allyl)rhodium(III) 17033. Trinuclear Palladium(II) Acetate 171Chapter Five MAIN GROUP COMPOUNDS AND LIGANDS 17434. Monocarbaborane Anions with 10 or 12 Vertices 174A. Tetraethylammonium arachno-6-Carba-decaboranate(14) 176B. Tetraethylammonium closo-2-Carba-decaboranate(10) 177C. Tetraethylammonium closo-1-Carba-decaboranate(10) 178D. Tetraethylammonium closo-1-Carba-dodecaboranate(12) 179E. Tetraethylammonium nido-6-Phenyl-6-carbadecaboranate(12) 180F. Tetraethylammonium closo-2-Phenyl-2-carbadecaboranate(10) 181G. Tetraethylammonium closo-1-Phenyl-1-carbadecaboranate(10) 182H. Tetraethylammonium closo-1-Phenyl-1-carbadodecaboranate(12) 18335. Tetrakis(5-tert-butyl-2-hydroxyphenyl)ethene 186A. 5,50-Di-tert-butyl-2,20-dimethoxybenzophenone 187B. Titanium Trichloride 1,2-Dimethoxyethane (1:1.5) 189C. Tetrakis(5-tert-butyl-2-methoxyphenyl)ethene 189D. Tetrakis(5-tert-butyl-2-hydroxyphenyl)ethene 19236. Electrochemical Synthesis of Tetraethylammonium Tetrathiooxalate 19537. Mid-Infrared Emitting Lead Selenide Nanocrystal Quantum Dots  198A. Lead Selenide NQDs Emitting at 2.5 μm (0.50 eV) 199B. Lead Selenide NQDs Emitting at 2.8 μm (0.44 eV) 200C. Lead Selenide NQDs Emitting at 3.3 μm (0.38 eV) 201D. Lead Selenide NQDs Emitting at 3.5 μm (0.35 eV) 201Chapter Six TEACHING LABORATORY EXPERIMENTS 20338. Tetra(acetato)dichromium(II) Dihydrate 20339. Keggin Structure Polyoxometalates  210A. Tri(ammonium) 12-Molybdophosphate 211B. 12-Tungstosilicic Acid   212C. 12-Tungstophosphoric Acid 214D. 12-Molybdophosphoric Acid   21540. Quadruply Metal–Metal Bonded Complexes of Rhenium(III) 217A. Tetrabutylammonium Perrhenate(VII)  218B. Bis(tetrabutylammonium) Octachlorodirhenate(III) 219C. Tetra(acetato)dichlorodirhenium(III) 22141. Bis[bis(triphenylphosphoranylidene)ammonium] Undecacarbonyltriferrate(2