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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 |
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| Authors: | Aresta Michele Tommasi Immacolata Quaranta Eugenio Fragale Carlo Mascetti Joëlle Tranquille Michel Galan Florence Fouassier Monique |
| Institution: | 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. |
| 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). |
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