CATALYTIC OXIDATION OF ALCOHOLS TO ESTERS WITH Ru3(CO)12

Article abstract of DOI:10.1016/0022-328X(84)85013-5

Ru3(CO)12 is an efficient homogeneous catalyst precursor for the conversion 2RCH2OH-->RCO2CH2R.With aliphatic primary alcohols and benzylic alcohols yields and selectivities of ca. 90percent are obtained.The reaction requires a hydrogen acceptor molecule; triple bonds and activated double bonds, as well as ketones and aldehydes, function as H-acceptors.The reaction proceeds in two steps, with an aldehyde intermediate which subsequently oxidatively couples with an alcohol to generate an ester.In most cases the aldehyde is present in a steady state concentration implying the presence of an equilibrium system.A disproportionation alcohol <*> aldehyde is a component of the above system.A catalytically active intermediate complex, Ru(CO)6(Ph2C2), was isolated when Ph2C2 was used as an acceptor.