Mechanism of formation of peroxocarbonates RhOOC(O)O(Cl)(P)(3) and their reactivity as oxygen transfer agents mimicking monooxygenases. The first evidence of CO2 insertion into the O-O bond of Rh(eta(2)-O-2) complexes

Extended labeling experiments have shown that formation of rhodium peroxocarbonate from CO2 and [RhCl(eta(2)-O-2)(P)(3)] (P is PEt(2)Ph or PEtPh(2)) proceeds through O-O bond cleavage and CO2 insertion. O-transfer to ancillary phosphine ligand to give R(3)P=O selectively (>85%) involves the Ph-linked O atom of the peroxo group of RhCl(CO4)(P)(3).