title: Mechanism of Formation of Peroxocarbonates RhOOC(O)O(Cl)(P)(3) and Their Reactivity as Oxygen Transfer Agents Mimicking Monooxygenases. The First Evidence of CO(2) Insertion into the O-O Bond of Rh(eta(2)-O(2)) 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).
authors.affiliation: Dipartimento di Chimica and Centro CNR-MISO, Università di Bari, Campus Universitario, 70126 Bari, Italy, and Laboratoire de Spectroscopie Moléculaire et Cristalline, U.R.A. 124 CNRS, 351 Cours de la Libération, 33405 Talence, France.
authors.forename: Michele
authors.initials: M
authors.lastname: Aresta
authors.forename: Immacolata
authors.initials: I
authors.lastname: Tommasi
authors.forename: Eugenio
authors.initials: E
authors.lastname: Quaranta
authors.forename: Carlo
authors.initials: C
authors.lastname: Fragale
authors.forename: Joëlle
authors.initials: J
authors.lastname: Mascetti
authors.forename: Michel
authors.initials: M
authors.lastname: Tranquille
authors.forename: Florence
authors.initials: F
authors.lastname: Galan
authors.forename: Monique
authors.initials: M
authors.lastname: Fouassier