Inorganic Chemistry, Vol.35, No.14, 4254-4260, 1996
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).
Keywords:DIOXIDE COORDINATION CHEMISTRY;RAY CRYSTAL-STRUCTURES;CARBON-DIOXIDE;TRIMETHYLPHOSPHINE COMPLEXES;DIOXYGEN;RHODIUM