Can Manganese(III)‐Iodosylarene Act as an Oxidant Alongside High‐Valent Manganese(V)‐Oxo Complexes?. Issue 11 (23rd March 2018)

• Record Type: Journal Article
• Authors: Kang, Yiran; Wang, Fang; Reinhard, Fabián G. Cantú; Xia, Chungu; de Visser, Sam P.; Wang, Yong
• Is Part Of: ChemistrySelect. Volume 3:Issue 11(2018)
• Page Start: 3208
• Page End: 3213
• Publication Date: 2018-03-23
• Subjects: biomimetic models -- manganese -- nonheme -- reactivity -- sulfoxidation; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/slct.201800678
• Languages: English
• ISSNs: 2365-6549

Abstract

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, the use of molecular oxygen is challenging and instead addition of iodosylarenes as terminal oxidants generates 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 that actually there are multiple isomeric iodosylarene complexes in solution and a number of those react with substrates with rate‐determining barriers at par with high‐valent metal‐oxo species. In particular, the [Mn III (PhIO)], [Mn V (O)(PhIO)] and [Mn IV (O)‐I(Ph)‐O ] complexes are identified as competitive oxidants and as such care should be taken with interpreting experimental rate constants. Abstract : Computational modelling on thioanisole oxidation by a Mn(III) complex in the presence of iodosylbenzene was studied. The work shows that the iodosylbenzene reacts on the manganese center forming four different stable local minima that all can react with substrate. Our work highlights the versatility of working with iodosylbenzene as a terminal oxidant.