Electron transfer oxidation of organic compounds. Part III. Oxidation of cyclohexanone by the hexachloroiridate(IV) anion and by related species
- 1 January 1970
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society B: Physical Organic
- p. 626-631
- https://doi.org/10.1039/j29700000626
Abstract
Evidence is presented from kinetic and product studies that the first step in the one-equivalent oxidation of the enol of cyclohexanone by the hexachloroiridate(IV) anion is an outer-sphere electron transfer which gives rise to the hexachloroiridate(III) anion and a 2-oxocyclohexyl radical. The latter then reacts with a further iridate(IV) ion by an inner-sphere (i.e., ligand transfer) mechanism, to give 2-chlorocyclohexanone and aquopentachloroiridate(III). Oxygen and acrylonitrile can both compete with iridium(IV) for the free radical. The oxidations of cyclohexanone by aquopentachloro-, diaquotetrachloro-, and hexabromo-iridate(IV) are very similar to the oxidation by hexachloroiridate(IV). The redox potentials of the complexes involved have been redetermined.Keywords
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