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DOI: 10.1039/A706576K (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 439-446

New organoarsino-bridged cobalt carbonyl complexes derived from reactions of [Co2(CO)8] or [Co2(µ-alkyne)(CO)6] with cyclo-(AsPh)6

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Rohini M. De Silva, Martin J. Mays, John E. Davies, Paul R. Raithby, Moira A. Rennie and Gregory P. Shield

Abstract

Reaction of hexaphenylcyclohexaarsane (PhAs)6 with [Co2(CO)8] in toluene at ambient temperature resulted in As–As bond cleavage and the new complexes [Co4(µ4-AsPh)2(CO)10] 1 and [Co4(µ3-AsPh)(µ4-η2∶η2∶η1-As4Ph4)(CO)10] 2. In contrast, reaction of cyclo-(PhAs)6 with the alkyene-bridged complexes [Co2(µ-R1C[triple bond, length half m-dash]CR2)(CO)6] in toluene or in benzene at 65 °C afforded the new complexes [Co2(µ-R1C[triple bond, length half m-dash]CR2){µ-cyclo-(PhAs)6}(CO)4] (R1 = R2 = H 3; or Ph 4 and 5 (isomers); R1 = Ph, R2 = H 6; R1 = Me, R2 = H 7) in which the As6 ring remains intact. All seven products have been characterised spectroscopically and, in addition, compounds 1–4 have been structurally characterised by X-ray diffraction analysis. The molecular structure of 1 comprises a rectangle of cobalt atoms capped above and below the plane by two quadruply bridging AsPh ligands, giving a pseudo-octahedral Co4As2 core. The molecular structure of 2 consists of two discrete Co2(CO)5 units linked by an As4Ph4 chain and an AsPh unit. In complexes 3–7 the six-membered As6 ring remains intact and acts as a bidentate bridging ligand replacing two equatorial carbonyl groups, one on each Co atom.

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