Mechanism of Oxidation of (olefin)Rh I  and ‐Ir I  Complexes by H 2 O 2 | Zendy

Budzelaar Peter H. M. | Zendy; Blok Arno N. J. | Zendy

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Mechanism of Oxidation of (olefin)Rh I and ‐Ir I Complexes by H 2 O 2

Author(s) -

Budzelaar Peter H. M.,

Blok Arno N. J.

Publication year - 2004

Publication title -

european journal of inorganic chemistry

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 0.667

H-Index - 136

eISSN - 1099-0682

pISSN - 1434-1948

DOI - 10.1002/ejic.200300546

Subject(s) - chemistry , heterolysis , deprotonation , olefin fiber , bond cleavage , peroxide , medicinal chemistry , reaction mechanism , photochemistry , catalysis , organic chemistry , ion

A DFT study of the oxidation of (tpa)M I (C 2 H 4 ) + and (dpa‐R)M I (cod) + complexes (M = Rh, Ir) by H 2 O 2 indicates that the reaction starts with heterolytic cleavage of the peroxide O−O bond, leading to M III (olefin)(OH) 2+ species. These can then undergo cyclisation, followed by deprotonation to oxetanes. In the oxidation of COD complexes, further cyclisation to internal ethers has a modest barrier, and the observed products (ethers for Rh, oxetanes for Ir) are suggested to be the thermodynamic ones. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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