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A Chromium(III)-Superoxo Complex as a Three-Electron Oxidant with a Large Tunneling Effect in Multi-Electron Oxidation of NADH Analogues

Title
A Chromium(III)-Superoxo Complex as a Three-Electron Oxidant with a Large Tunneling Effect in Multi-Electron Oxidation of NADH Analogues
Authors
Devi, TaraliLee, Yong-MinJung, JieunSankaralingam, MuniyandiNam, WonwooFukuzumi, Shunichi
Ewha Authors
남원우이용민Shunichi Fukuzumi정지은
SCOPUS Author ID
남원우scopus; Shunichi Fukuzumiscopus; 정지은scopus
Issue Date
2017
Journal Title
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
ISSN
1433-7851JCR Link1521-3773JCR Link
Citation
vol. 56, no. 13, pp. 3510 - 3515
Keywords
chromium(III)-superoxo complexeshydride transferhydrogen atom transferNADH analoguesthree-electron oxidant
Publisher
WILEY-V C H VERLAG GMBH
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
Metal-superoxo species are involved in a variety of enzymatic oxidation reactions, and multi-electron oxidation of substrates is frequently observed in those enzymatic reactions. ACr(III)-superoxo complex, [Cr-III(O-2)(TMC)(Cl)](+) (1; TMC=1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), is described that acts as a novel three-electron oxidant in the oxidation of dihydronicotinamide adenine dinucleotide (NADH) analogues. In the reactions of 1 with NADH analogues, a Cr-IV-oxo complex, [Cr-IV(O)(TMC)(Cl)](+) (2), is formed by a heterolytic O-O bond cleavage of a putative Cr-II-hydroperoxo complex, [Cr-II(OOH)(TMC)(Cl)], which is generated by hydride transfer from NADH analogues to 1. The comparison of the reactivity of NADH analogues with 1 and p-chloranil (Cl(4)Q) indicates that oxidation of NADH analogues by 1 proceeds by proton-coupled electron transfer with a very large tunneling effect (for example, with a kinetic isotope effect of 470 at 233 K), followed by rapid electron transfer.
DOI
10.1002/ange.201611709
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자연과학대학 > 화학·나노과학전공 > Journal papers
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