Cocatalyzed oxidation of carbon monoxide and triphenylphosphine using complexes derived from hexarhodium hexadecacarbonyl as homogeneous catalyst. Characterization of rhodium carbonyl intermediates, oxygen-18 labeling to identify oxygen atom sources, and observation of catalyzed oxygen atom exchange between carbon dioxide and water

Hexarhodium hexadecacarbonyl, Rh6(CO)16, will cocatalyze a reaction with molecular oxygen involving the conversion both of carbon monoxide to carbon dioxide and of triphenylphosphine (PPh3) to triphenylphosphine oxide (OPPh3). Solution infrared spectroscopy in the carbonyl region in benzene solvent shows that the catalytic cycle passes through the red Rh2(CO)2-(PPh3)4(C6H6)2, the yellow Rh2(CO)6(PPh3)2, and the red Rh4(CO)10(PPh3)2. Final return to Rh6(CO)16 does not occur under the ambient temperature and pressure conditions used but can be achieved by elevating these conditions. Addition of carbon dioxide to a mixture of Rh6(CO)16, CO, and PPh3 in the presence of added 18OH2 shows that the rhodium compounds will catalyze oxygen exchange between carbon dioxide and the oxygen atom of water. A pathway for equilibration of oxygen isotope in the catalyzed conversion of coordinated carbonyl to carbon dioxide via metallocarboxylate intermediates is proposed. The equilibration of oxygen isotope from water into carbon dioxide catalyzed by rhodium carbonyl clusters is suggested to proceed via hydroxyrhodium intermediates. 3 figures, 3 tables