Unique Evidence for a RhIII to RhI Reduction by Deoxygenation of a Carbonate Moiety to CO2 by an Out-of-Sphere Phosphane

RhIII carbonate generated from either a peroxocarbonate complex [RhCl(CO4)(PR3)3] or [RhCl3(PR3)3] and Na2CO3, is reduced to RhI by deoxygenation of the carbonate moiety to CO2 by an out-of-sphere phosphane. The reaction takes place in mild conditions and is implied in the catalytic activity shown by RhI in the oxidation of styrene with O2/CO2 mixtures.