Mechanism of oxidation of (olefin)Rh-I and -Ir-I complexes by H2O2
SourceEuropean Journal of Inorganic Chemistry, 2004, 11, (2004), pp. 2385-2391
Article / Letter to editor
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European Journal of Inorganic Chemistry
A DFT study of the oxidation of (tpa)M-I(C2H4)(+) and (dpa-R)M-I(cod)(+) complexes (M = Rh, Ir) by H2O2 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. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
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