Phosphides, synthesis

Cyanate condensation products of carbohydrazide, synthesis 11 Thiosemicarbazide, synthesis 12 Dithiocarbamates of selenium(II) and tellurium (II), synthesis 32 Aluminum phosphide, synthesis 7 Phosphorus(III) fluoride, synthesis 49... 

Douglas T and Theopold K H 1991 Molecular precursors for indium phosphide and synthesis of small lll-V semiconductor clusters in solution inorg. Chem. 30 594... 

Such reactions are discussed at appropriate points throughout the book as each individual compound is being considered. A particularly important set of reactions in this category is the synthesis of element hydrides by hydrolysis of certain sulfides (to give H2S), nitrides (to give NH3), phosphides (PH3), carbides (C Hm), borides (B Hm), etc. Useful reviews are available on hydrometallurgy (the recovery of metals by use of aqueous solutions at relatively low temperatures), hydrothermal syntheses and the use of supercritical water as a reaction medium for chemistry. 

Low-temperature solvents are not readily available for many refractory compounds and semiconductors of interest. Molten salt electrolysis is utilized in many instances, as for the synthesis and deposition of elemental materials such as Al, Si, and also a wide variety of binary and ternary compounds such as borides, carbides, silicides, phosphides, arsenides, and sulfides, and the semiconductors SiC, GaAs, and GaP and InP [16], A few available reports regarding the metal chalcogenides examined in this chapter will be addressed in the respective sections. Let us note here that halide fluxes provide a good reaction medium for the crystal growth of refractory compounds. A wide spectrum of alkali and alkaline earth halides provides... 

Sweet JD, Casadonte DJ (2001) Sonochemical synthesis of iron phosphide. Ultrason Sono-chem 8 97-101... 

In 1989 we reported on the synthesis and structure of the first l,3-diphospha-2-sila-allylic anion 3a [4], mentioning its value as a precursor for phosphino-silaphosphenes. In analogy to 3a we obtained the anions 3b-f [5] by treatment of 4 equivalents of the lithium phosphide 1 with the adequately substituted RSiC, of which 3b and 3c were investigated by X-ray analyses. The very short P-Si bond lengths (2.11-2.13 A) of 3a-c and the almost planar arrangement of Pl-Sil-P2-Lil indicate the cr-character of the Lithium P-Si-P allyl complex. 

T. Inada and T. Fukuda, Direct Synthesis and Growth of Indium Phosphide by the Liquid Phosphorous Encapsulated Czochralski Method O. Oda, K. Katagiri, K. Shinohara, S. Katsura, Y. Takahashi, K. Kainosho, K. Kohiro, and R. Hirano, InP Crystal Growth, Substrate Preparation and Evaluation K. Tada, M. Tatsumi, M. Morioka, T. Araki, and T. Kawase, InP Substrates Production and Quality Control... 

An unusual mixed lithium phosphide/lithium alkyl aggregate has been reported as arising from an attempted synthesis of Li PH(mes ) (46). Initial treatment of phosphorus trichloride with Li(mes ) is reported to give a mixture of the desired product, (mes )PCl2, and the side product (mes )Cl (via Li/Cl exchange) in an approximately 2 1 ratio. Reduction of this mixture with LiAlH4, followed by treatment with BuLi, then leads to rapid formation of Li PH(mes ), accompa-... 

Heterometallic alkali metal phosphide complexes with transition metals have also been reported. The complex [(Cy2P)3Hf(ju.-PCy2)2Li (DME)] results from the reaction of LiPCy2 with HfCl4(THF) (98). This complex persists in solution. Jones et al. have reported the synthesis and reactivity toward a range of electrophiles of a series of lithium di-t-butylphosphido(alkyl)cuprates [RCu(PBu2)Li] (R = Me,... 

In comparison to alkali metal complexes of (di)organophosphide ligands, complexes of these metals with (di)organoarsenide ligands are relatively rare and few have been structurally characterized. This dearth of structural information is perhaps due in part to the relatively low importance of such complexes in inorganic and organic synthesis and to the lower stability (both thermal and photolytic) of arsenide complexes compared to their phosphide analogues. 

Trofimov, B.A. Gusarova, N.K., Malysheva, S.F., Rakhmatulina, T.N., Voronkov, M.G., Dmitriev, V.I., and Shaikhudinova, S.I., Superbase-induced generation of phosphide and phosphinite ions as applied in organic synthesis, Phosph., Sulf., Silic. Relat. Elem., 55, 271, 1991. 

Clark, P.W. and Mulraney, B.J., Synthesis and physical properties of chlo-rodi(o-tolyl)phosphine, lithium di(o-tolyl)phosphide and the diphosphine series (o-tolyl)2P(CH2)nP(o-tolyl) (n = 1-4,6,8), /. Organomet. Chem., 217,51,1981. 

By far the most ubiquitous intermediates in synthesis of this class of phosphines are the alkali metal phosphides which can be prepared by either the KOH/DMSO method, by reaction of tertiary phosphines or chlorophosphines with alkali metals, or in the reaction of BuLi with appropriate secondary or tertiary phosphines. A number of the ligands in Figures 6 and 7 were prepared this way (60-69,72-74). 

Silylated aminoiminophosphane, reaction with hexafluoroacetone, 30 238 Silylated cyclotetraphosphanes, 31 198 reactions with lithium alkyls and lithium phosphides, 31 204-212 Silylated tri- and tetraphosphanes reactions with lithium alkyls and lithium phosphides, 31 199-212 synthesis via lithiated diphosphanes, 31 194-198... 

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