Abstract
Protonation of the methylene-bridged complex [RhRu(CO)4(μ-CH2)(dppm)2][CF3SO3] (1) at −80 °C yields an asymmetrically bridged methyl complex in which the methyl ligand is σ-bound to Ru while being involved in an agostic interaction with Rh. Warming to −40 °C results in migration of the methyl group to a terminal site on Rh, and further warming to 0 °C results in migratory insertion to give the acetyl-bridged complex [RhRu(OSO2CF3)(CO)2(μ-C(CH3)O)(μ-CO)(dppm)2][CF3SO3] (4), in which the acetyl carbon is bound to Rh and its oxygen is bound to Ru. At ambient temperature one carbonyl is lost from 4 to give [RhRu(OSO2CF3)(CO)2(μ-C(CH3)O)(dppm)2][CF3SO3] (5). Carbon-13 NMR spectroscopy and the X-ray structures of both acetyl-bridged products suggest significant carbene character in the acyl carbon. Attempts to obtain methyl and subsequently acetyl species by methylene insertion into metal−hydride bonds of the appropriate precursors [RhRu(X)(CO)4(μ-H)(dppm)2][X] (X- = CF3SO3-, BF4-) failed, with these hydride sp...
Published Version
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