A Mononuclear Non-heme Manganese(III)-Aqua Complex as a New Active Oxidant in Hydrogen Atom Transfer Reactions

Muniyandi Sankaralingam, Yong Min Lee, Deepika G. Karmalkar, Wonwoo Nam, Shunichi Fukuzumi

Research output: Contribution to journalArticlepeer-review

19 Scopus citations

Abstract

A mononuclear non-heme Mn(III)-aqua complex, [(dpaq)MnIII(OH2)]2+ (1, dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate), is capable of conducting hydrogen atom transfer (HAT) reactions much more efficiently than the corresponding Mn(III)-hydroxo complex, [(dpaq)MnIII(OH)]+ (2); the high reactivity of 1 results from the positive one-electron reduction potential of 1 (Ered vs SCE = 1.03 V), compared to that of 2 (Ered vs SCE = -0.1 V). The HAT mechanism of 1 varies between electron transfer followed by proton transfer and one-step concerted proton-coupled electron transfer, depending on the one-electron oxidation potentials of substrates. To the best of our knowledge, this is the first example showing that metal(III)-aqua complex can be an effective H-atom abstraction reagent.

Original languageEnglish
Pages (from-to)12695-12699
Number of pages5
JournalJournal of the American Chemical Society
Volume140
Issue number40
DOIs
StatePublished - 10 Oct 2018

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