A Mononuclear Non-heme Manganese(III)-Aqua Complex as a New Active Oxidant in Hydrogen Atom Transfer Reactions
- 주제(기타) Chemistry, Multidisciplinary
- 설명문(일반) [Sankaralingam, Muniyandi; Lee, Yong-Min; Karmalkar, Deepika G.; Nam, Wonwoo; Fukuzumi, Shunichi] Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea; [Fukuzumi, Shunichi] Meijo Univ, Fac Sci & Engn, Nagoya, Aichi 4688502, Japan
- 등재 SCIE, SCOPUS
- 발행기관 AMER CHEMICAL SOC
- 발행년도 2018
- URI http://www.dcollection.net/handler/ewha/000000155657
- 본문언어 영어
- Published As http://dx.doi.org/10.1021/jacs.8b07772
초록/요약
A mononuclear non-heme Mn(III)-aqua complex, [(dpaq)Mn-III(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)Mn-III(OH)](+) (2); the high reactivity of 1 results from the positive one-electron reduction potential of 1 (E-red vs SCE = 1.03 V), compared to that of 2 (E-red 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.
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