Arsine complexes ruthenium

A few cyano phosphine and arsine complexes of ruthenium(II) have been reported. These include tra s-[RuH(CN)(dmpe)2] (dmpe = Me2P(CH2)2PMe2) obtained from the corresponding chloro complex and aqueous KCN43 or more recently by treatment of [RuH(2-np)(dmpe)2] (2-np = 2-naphthyl) with HCN. The latter gives a 85% cis, 15% trans isomer mixture ( H NMR evidence).44... 

Coe, B.J., Beyer, T., Jeffery, J.C., Coles, S.J., Gelbrich, T., Hursthouse, M.B.. Light, M.E. A spectroscopic, electrochemical and structural study of polarizable, dipolar ruthenium(II) arsine complexes as models for chromophores with large quadratic non-linear optical responses. J. Chem. Soc., Dalton Trans. 797-803 (2000)... 

The chemistry of these compounds has not been investigated in detail. Scheme 12 summarizes some of the chemistry that has been established for the ruthenium complex RugClCO) (192). In general, the octahedral metal-carbido skeleton is maintained, substitution reactions occurring with phosphine, phosphites, and arsine ligands. Base attack leads to the production of the anion [Ru8C(CO)16P, which is... 

C1bHi5As, Arsine, triphenyl-iron complex, 26 61 C H 5OjP, Triphenyl phosphite ruthenium complex, 26 178 CuHijP, Phosphine, triphenyl-cobalt complex, 26 190—197 cobalt-gold-ruthenium, 26 327 gold complex, 26 90, 325, 326 gold-manganese complex, 26 229 iridium complexes, 26 117-120, 122-125, 201, 202... 

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. 

There are now a substantial number of nitrido complexes of osmium(VI) and osmium(IV) as well as the osmiamate ion [OsVII 03N]. In addition to the ammine and ethylenediamine complexes, much recent work has been carried out on the bipy, phen and terpy complexes, often in connection with research into the photodissociation of water. The nitrosyl chemistry of the element, though seemingly not as extensive as that of ruthenium, has received much attention, and there has been considerable work on the phosphine, arsine and stibine complexes. 

AsFe04C22H,5, lron(0), tetracarbonyl(tri-phenylarsine)-, 26 61, 28 171 AsjCijHij, Arsine, l,2-phenylenebis(di-methyl-, gold complex, 26 89 nickel complex, 28 103 AsjCljNRuSCjgHjo, Ruthenium(II), tri-... 

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... 

Khan MMT, Venkatasubramanian K, Shirin Z, Bhadbhade MM (1992) Mixed-ligand complexes of ruthenium(in) and ruthenium(II) with ethylenediaminetetraacetate and bidentate phosphines and arsines. J Chem Soc Dalton Trans 885-890... 

More limited investigations of the oxidation of triorganoarsines in the presence of transition metal complexes have been carried out but it appears that many of the same complexes which catalyze phosphine oxidation are also effective for arsines. The ruthenium complex, [Ru(NCSXN0XPPh3)2(02)], for example, has been found to be an efficient catalyst for the oxidation of triphenylarsine [79] the initial rate of oxidation being three to four times greater than the corresponding rate for triphenyl-phosphine oxidation under the same conditions. However, the rate of this oxidation was rapidly diminished by decomposition of the catalyst so that in a short time ca. 30 min) the catalyst was virtually ineffective. 

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