Cadmium phosphine complexes

Codeposition of silver vapor with perfluoroalkyl iodides at -196 °C provides an alternative route to nonsolvated primary perfluoroalkylsilvers [272] Phosphine complexes of trifluaromethylsilver are formed from the reaction of trimethyl-phosphme, silver acetate, and bis(trifluoromethyl)cadmium glyme [755] The per-fluoroalkylsilver compounds react with halogens [270], carbon dioxide [274], allyl halides [270, 274], mineral acids and water [275], and nitrosyl chloride [276] to give the expected products Oxidation with dioxygen gives ketones [270] or acyl halides [270] Sulfur reacts via insertion of sulfur into the carbon-silver bond [270] (equation 188)... 

In the case of much more labile complex systems, the NMR spectrum yields a single peak at the position which corresponds to the weighted average of the chemical shift values characterizing each successive complex and their individual abundances at equilibrium. The cadmium-phosphinate system is such a labile complex system. It has been studied by monitoring the shift of the single peak formed, the coordination be-... 

Recently Zn NMR studies of imidazole and carboxylate complexes and the thermolysin-zinc complex have been described and Cd NMR studies of a wide range of complexes have been reported CdNMR data for pyridine adducts of Cd /3-diketonates show the influence of the sulfur and nitrogen donors on the chemical shift Cadmium NMR studies on cadmium fluoride have also been reported. A CdNMR study of Cd-enriched phosphine oxide complexes has been reported " and a multinuclear NMR investigation and Cd) of cadmium dithiophosphate complexes has been described. ... 

Darensbourg DJ, Wildeson JR, Yarbrough JC, Reibenspies JH (2000) Bis 2,6-difluorophen-oxide dimeric complexes of zinc and cadmium and their phosphine adducts lessons learned relative to carbon dioxide/cyclohexene oxide alternating copolymerization processes catalyzed by zinc phenoxides. J Am Chem Soc 122 12487-12496... 

Many studies on the direct reaction of methyl chloride with silicon-copper contact mass and other metal promoters added to the silicon-copper contact mass have focused on the reaction mechanisms.7,8 The reaction rate and the selectivity for dimethyldichlorosilane in this direct synthesis are influenced by metal additives, known as promoters, in low concentration. Aluminum, antimony, arsenic, bismuth, mercury, phosphorus, phosphine compounds34 and their metal complexes,35,36 Zinc,37 39 tin38-40 etc. are known to have beneficial effects as promoters for dimethyldichlorosilane formation.7,8 Promoters are not themselves good catalysts for the direct reaction at temperatures < 350 °C,6,8 but require the presence of copper to be effective. When zinc metal or zinc compounds (0.03-0.75 wt%) were added to silicon-copper contact mass, the reaction rate was potentiated and the selectivity of dimethyldichlorosilane was enhanced further.34 These materials are described as structural promoters because they alter the surface enrichment of silicon, increase the electron density of the surface of the catalyst modify the crystal structure of the copper-silicon solid phase, and affect the absorption of methyl chloride on the catalyst surface and the activation energy for the formation of dimethyldichlorosilane.38,39 Cadmium is also a structural promoter for this reaction, but cadmium presents serious toxicity problems in industrial use on a large scale.41,42 Other metals such as arsenic, mercury, etc. are also restricted because of such toxicity problems. In the direct reaction of methyl chloride, tin in... 

CF3H, Methane, trifluoro-cadmium complex, 24 55 mercury complex, 24 52 CF3NOS, Imidosulfurous difluoride, (fluorocarbonyl)-, 24 10 CH2, Methylene ruthenium complex, 25 182 CH2CI4P2, Phosphine, methylenebis-(dichloro)-, 25 121 CH3, Methyl cobalt complexes, 23 170 mercury complexes, 24 143-145 platinum complex, 25 104, lOS CNO, Cyanato silicon complex, 24 99 CN2OS2, l,3k, 2,4-Dithiadiazol-5-one, 25 53 CO, Carbon monoxide chromium complexes, 21 1, 2 23 87 cobalt complex, 25 177 cobalt, iron, osmium, and ruthenium complexes, 21 58-65 cobalt-osmium complexes 25 195-197 cobalt-ruthenium cluster complexes, 25 164... 

Tributylphosphine sulfide has been used as a co-catalyst with dicobalt octacarbonyl for the Pawson-Khand reaction. Thermolysis of a mixture of cadmium chloride and trioctylphosphine sulfide at 250 °C has been used as a route to the formation of nanocrystalline cadmium sulfide." A complex of triphenylphosphine sulfide with a silver-tungsten-iodine acceptor has been characterised by X-ray studies. Ferrocenylphosphine chalcogenides have attracted considerable interest as ligands. Complexes of the monophosphino-phosphine sulfide (269) with rhodium have been characterised." The disulfide (270) forms complexes with both gold(i) and gold(iii) acceptors," and a silver(i) complex of the diselenide (271) has been prepared. ... 

A number of stannyl-zinc and -cadmium compounds have been prepared by reaction of a tin-alkali metal compound with a zinc or cadmium halide, or a tin hydride with an alkyl-zinc or -cadmium compound. The coordination of a ligand such as a triphenyl-phosphine, TMEDA, or bipyridyl, or a solvating solvent such as DME, both enhances the nucleophilicity of the alkyl group in the alkylmetallic compounds and stabilises the stannylmetallic product. Thus triphenyltin hydride reacts with diethylzinc or diethylcad-mium in pentane or benzene with separation of metallic zinc or cadmium, but with a preformed complex, or in a coordinating solvent, the distannylmetallic compound is formed (e.g. equation 19-32). 

These Fp-alkene complexes react with a variety of other nucleophiles,3 5 including water, alcohols, amines,3 6 phosphines, and thiols as well as carbon nucleophiles (enamines, organocuprates, enolates),3 2,3l8 and dialkyl cadmium reagents.3 9 Diene complexes such as 487 were converted to the corresponding cationic complexes (488), for example, and reaction with malonate gave 489. The iron complex was removed with trimethylamine N-oxide (Me N-O) to give 490.320... 

Lanthanide-, tellurium(Il)- and tellurium(IV), as well as, cadmium(II) and zink(II) complexes of tertiary phosphine chalcogenides were also described. ... 

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