Chromium complex compounds with acetonitrile

The mechanisms of the oxidation of phosphines and arsines by chromium(VI) have been examined both in solution and on a diatomite support. Kinetic parameters are presented for both supported and solution reactions. A ruthenium complex of 1,4,8,1 l-tetramethyl-l,4,8,ll-tetraazacyclotetradecane has been utilized to oxidize triphenylphosphine in acetonitrile. Although a limited temperature range was utilized, a AH value of 8.7 0.8 kcal mor and a A5 value of -20 2 cal K mor were calculated. The secondary phosphine oxides, HP(0)R (R = n-butyl, isobutyl, cyclohexyl) and 9H-9-phosphabicyclononane-9-oxide, react with cobaltocene to yield dihydrogen and cobalt(I) compounds. With the less bulky phosphorus ligands at elevated temperatures trinuclear cobalt(III, II) complexes may be obtained. Arsenious acid may be utilized to catalyze the oxygen atom... 

Bis[dw-butyLphosphano] tellurium replaces norbornadiene, cycloheptatriene, acetonitrile, and dimethyl(methylene)oxosulfurane in chromium, molybdenum, and tungsten complexes. The P —Te compound acts as a bidentate ligand with the two phosphorus atoms coordinated to the metal atom1. The tetracarbonylchromium complex [R = CH(CH3)J can be recrystallized without loss of tellurium2. 

Various other solvate complexes can be obtained, when transition, metals are reacted with the free halogens in acetonitrile . In this way TiCl4(AN)2, TiBr4(AN)2 and a polyhalide [Ti(AN)6] [Isis are produced. Chlorine, bromine and iodine oxidize vanadium to trivalent compounds, namely VCl3(AN)3AN, [VBr2(AN)4]Br and the polyiodide [V(AN)6][Is]s- With chromium CrCls(AN)3AN, a bromide of variable (composition and [Crl2(AN)4]I are obtaincd. ... 

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