Reactions of metal ion complexes with hydrocarbons. Part II. Some acetoxylation, methylation and related reactions of palladium(II) and lead(IV)

Abstract

The acetoxylations of Pb(OAc)₄ and Pd(OAc)₂ have been examined and extended to include benzene, toluene, xylenes, and hexamethylbenzene as substrates. Acetic acid was used as solvent with various concentrations of acetate ion. The reactions in strongly basic solution are inhibited by oxygen and for these a radical-chain reaction scheme has been suggested in which Pb^III and Pd^I are chain-carrying intermediates. Careful exclusion of oxygen allows the reactions of Pb(OAc)₄ to take place at a much lower temperature than has been reported hitherto. Under conditions of inhibition by oxygen or in acid solution other reaction pathways become dominant. A brief comparison is made with the acetoxylations of cerium(IV), manganese(III), and mercury(II).