Arsine complexes chromium

Table 8 Tertiary Phosphine and Arsine Complexes of Chromium(0) Including Mixed...

AsAgFsSi6, Arsenate, hexafluoro-, bis-(cycZo-octasulfur)silver(l -h), 24 74 AsBrsFgS, Arsenate, hexafluoro-, tribromo-sulfur(IV), 24 76 AsQH, Arsine, dimethyl-molybdenum complex, 25 169 AsCigHis, Arsine, triphenyl-chromium complexes, 23 38 ASC24H10, Arsonium, tetraphenyl-... 

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... 

Although trialkyl- and triarylbismuthines are much weaker donors than the corresponding phosphoms, arsenic, and antimony compounds, they have nevertheless been employed to a considerable extent as ligands in transition metal complexes. The metals coordinated to the bismuth in these complexes include chromium (72—77), cobalt (78,79), iridium (80), iron (77,81,82), manganese (83,84), molybdenum (72,75—77,85—89), nickel (75,79,90,91), niobium (92), rhodium (93,94), silver (95—97), tungsten (72,75—77,87,89), uranium (98), and vanadium (99). The coordination compounds formed from tertiary bismuthines are less stable than those formed from tertiary phosphines, arsines, or stibines. 

The reactions of dihydrobilin (1,19-dideoxybiladiene-a, c) with transition metals are strongly influenced by the nature of the metal ion. Thus with Mn(OAc)3 or FeClj the corresponding metallocorrolates have been obtained in high yield, in the presence of chromium or ruthenium salts the reaction product isolated has been the metal free macrocycle, while coordination of rhodium requires the presence of an axial ligand such as a phosphine, arsine or amine [21]. Neutral pentacoordinated rhodium complexes have thus been obtained. Although analysis of the electronic spectra of the reaction mixtures demonstrated that cyclization of the open-chain precursor and formation of metallocorrolates occur even in the absence of extra ligands, no axially unsubstituted rhodium derivative has been reported. 

Interferences Metals or salts of metals such as chromium, cobalt, copper, mercury, molybdenum, nickel, palladium, and silver may interfere with the evolution of arsine. Antimony, which forms stibine, is the only metal likely to produce a positive interference in the color development with the silver diethyldithiocarbamate. Stibine forms a red color with silver diethyldithiocarbamate that has a maximum absorbance at 510 nm, but at 535 to 540 nm, the absorbance of the antimony complex is so diminished that the results of the determination would not be altered significantly. 

The mass spectra of bimetallic carbonyl metal compounds with cyclic arsine ligands have been discussed (Table 10). Molecular ion peaks are present for the pentamethyl-cyclopentaarsine containing complexes of chromium and tungsten, (AsMe)5[M(CO)]2 (186,188). Their decomposition includes CO and/or M(CO)5 loss giving rise to the ions (AsMe)sM2(CO) + (n = 0-9), (AsMe)sM(CO)/ (n = 0-5), M As Me-" and MAs Me+ (m = 2-4), MjAs Me, M AsMe -" (m = 2-4), MAs (w = 2-5), MAsjCH and AsMOj The latter is the most abundant in the mass spectra . ... 

Chromium hexacarbonyl reacts with Ph2AsCH2AsPh2 yielding a compound of stoichiometry Cr(CO)2(Ph2AsCH2AsPh2) 357) and with triarylphosphines yielding complexes of the type [Cr(CO)2L]2 [L = PPhg, P( i-tolyl)3, and P(p-tolyl)3] (31). The arsine and triphenyl-phosphine compounds have been shown by X-ray analysis to possess the structures (VII) and (VIII), respectively, in which a phenyl group is... 

C10H15N, Benzenemethanamine, N,N,4-trimethyl-, lithium complex, 26 152 C10H15P, Phosphine, diethylphenyl-, nickel complex, 28 101 platinum complex, 28 135 CioHigAsi, Arsine, 1,2-phenylenebis(dimethyl-, gold complex, 26 89 nickel complex, 28 103 CioHie, 1,3-Cyclopentadiene, 1,2,3,4,5-pen-tamethyl-, 28 317 chromium complex, 27 69 cobalt complexes, 28 273, 275 iridium complex, 27 19 samarium complex, 27 155 titanium complex, 27 62 ytterbium complex, 27 148 CioH,gBrN04S, Bicyclo[2.2.1]heptane-7-methanesulfonate, 3-bromo-1,7-di-methyl-2-oxo-, U.IRHENDO, ANTPi]-, ammonium, 26 24... 

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