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(η²-O₂) Complexes

Abstract

Extended labeling experiments have shown that formation of rhodium peroxocarbonate from CO(2) and [RhCl(eta(2)-O(2))(P)(3)] (P is PEt(2)Ph or PEtPh(2)) proceeds through O-O bond cleavage and CO(2) insertion. O-transfer to ancillary phosphine ligand to give R(3)P=O selectively (>85%) involves the Rh-linked O atom of the peroxo group of RhCl(CO(4))(P)(3).