Can Manganese(III)‐Iodosylarene Act as an Oxidant Alongside High‐Valent Manganese(V)‐Oxo Complexes?

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Abstract

Metalloenzymes often utilize a high-valent metal-oxo species in their catalytic cycle that is formed through a combination of reduction/proton transfer steps from O2. In biomimetic chemistry, by contrast, iodosylarenes are commonly used as terminal oxidants to generate these high valent metal-oxo intermediates. There has been controversy in the literature for many years, whether the iodosylarene (or one of its side-products in a reaction with a metal center) can act as an active oxidant. Herein, we present a comprehensive theoretical study on the thioanisole oxidation by a range of possible oxidants originating from a reaction mixture of a Mn(III) complex with iodosylbenzene. We show here, for the first time, that actually iodosylarene complexes can react with substrates themselves and hence are active oxidants. In particular, the [MnIII(PhIO)], [MnV(O)(PhIO)] and [MnIV(O)-I(Ph)-O•] complexes react with substrate via low energy oxygen atom transfer reactions

Bibliographical metadata

Original languageEnglish
JournalChemistry Select
Early online date23 Mar 2018
DOIs
StatePublished - 23 Mar 2018