Abstract
The preparation of trans-[Ru(CHO)(CO)(dppb)2][SbF6][dppb = 1,2-bis(diphenylphosphino)benzene] from hydridic reduction of trans-[Ru(CO)2(dppb)2][SbF6]2 is described. The formyl complex decomposes with first-order kinetics (t½= 28 min) at 30 °C to give exclusively trans-[RuH(CO)(dppb)2][SbF6]. Detailed studies of the decomposition reaction including the observation of initiation of free-radical polymerization of methyl methacrylate during the reaction lead to the postulation of rate-determining homolytic cleavage of the Ru–CHO bond. The low rate of initiation of polymerization, together with the high isotope effect for the decomposition (kH/kD= 2.3) and the failure to observe cross-over products during co-decomposition of trans-[Ru(13CHO)(13CO)(dppb)2][SbF6] and trans-[Ru(CDO)(CO)(dppb)2][SbF6], lead to the conclusion that another decomposition pathway, involving concerted H migration and CO loss in a six-co-ordinate complex, operates. These results are compared with those obtained for trans-[Ru(CHO)(CO)(dppe)2][SbF6][dppe = 1,2-bis(diphenylphosphino)ethane].
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