Franco Rivetti

Alkoxy carbonyl complexes of palladium and their role in alcohol carbonylation

Abstract The behaviour of phosphinepalladium(II) complexes in methanol/carbon monoxide systems has been investigated. Pd(COOCH 3 )(OAc)(PPh 3 ) 2 and Pd (COOCH 3 ) 2 (PPh 3 ) 2 have been isolated and characterized. A scheme is presented for the formation of oxalate esters in alcohol carbonylation in the presence of palladium complexes.

Alcohol carbonylation with palladium(II) complexes, effects of ligands, carbon monoxide, pressure and added bases

Abstract The carbonylation of methanol with carbon monoxide to dimethyl oxalate and dimethyl carbonate in the presence of palladium(II) acetate has been shown to be influenced by the ligands, the CO pressure and added base. With phosphines, the ligand influence appears to be related mainly to their electronic properties. Alkylphosphines inhibit carbonylation almost completely. Low CO pressures and the presence of tertiary amines enhance the formation of dimethyl carbonate. A scheme accounting for these findings is presented.