Unprecedented Reactivities of Highly Reactive Manganese(III)-Iodosylarene Porphyrins in Oxidation Reactions

Lina Zhang, Yong Min Lee, Mian Guo, Shunichi Fukuzumi, Wonwoo Nam

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

We report that Mn(III)-iodosylarene porphyrins, [MnIII(Porp)(sArIO)]+, are capable of activating the C-H bonds of hydrocarbons, including unactivated alkanes such as cyclohexane, with unprecedented reactivities, such as a low kinetic isotope effect, a saturation behavior of reaction rates, and no electronic effect of porphyrin ligands on the reactivities of [MnIII(Porp)(sArIO)]+. In oxygen atom transfer (OAT) reactions, the sulfoxidation of para-X-substituted thioanisoles by [MnIII(Porp)(sArIO)]+ affords a very unusual behavior in the Hammett plot with the saturation behavior of reaction rates and no electronic effect of porphyrin ligands on reactivities. The reactivities and mechanisms of [MnIII(Porp)(sArIO)]+ are then compared with those of the corresponding MnIV(Porp)(O) complex. The present study reports the first example of highly reactive Mn(III)-iodosylarene porphyrins with unprecedented reactivities in C-H bond activation and OAT reactions.

Original languageEnglish
Pages (from-to)19879-19884
Number of pages6
JournalJournal of the American Chemical Society
Volume142
Issue number47
DOIs
StatePublished - 25 Nov 2020

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