Oxidative addition reactions of complexed phosphine and arsine at platinum(0) complexes

The reactions of E(SiMe3)(3) with [W(CO)(5)thf] yield after alcoholysis in a one-pot reaction the complexes [(CO)(5)WEH3] (1) (E = P(a), As(b)). This procedure circumvents the direct use of gaseous phosphine and arsine, respe ctively. Complexes 1 react with [(C2H4)Pt(PPh3)(2)] in an oxidative additio n type reaction to form the heterometallic complexes [(PPh3)(2)Pt(H) {(mu - EH2)W(CO)(5)}]I (E = P(2), As(3)). Complexes 2 and 3 were obtained as mixtu res of their cis- and trans-isomers, in which the contents of the trans-iso mer dominates. The products were comprehensively spectroscopically characte rised, and the structures of the trans-complexes 2 and 3 were determined by X-ray crystal structure analysis.