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Switchover of the Mechanism between Electron Transfer and Hydrogen-Atom Transfer for a Protonated Manganese(IV)-Oxo Complex by Changing Only the Reaction Temperature

Title
Switchover of the Mechanism between Electron Transfer and Hydrogen-Atom Transfer for a Protonated Manganese(IV)-Oxo Complex by Changing Only the Reaction Temperature
Authors
Jung, JieunKim, SurinLee, Yong-MinNam, WonwooFukuzumi, Shunichi
Ewha Authors
남원우Shunichi Fukuzumi이용민정지은
SCOPUS Author ID
남원우scopus; Shunichi Fukuzumiscopus; 이용민scopusscopus; 정지은scopus
Issue Date
2016
Journal Title
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
ISSN
1433-7851JCR Link1521-3773JCR Link
Citation
vol. 55, no. 26, pp. 7450 - 7454
Keywords
bioinorganic chemistryelectron transferhydrogen atom transfermanganese(IV)-oxo complexmechanism switchover
Publisher
WILEY-V C H VERLAG GMBH
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
Hydroxylation of mesitylene by a nonheme manganese(IV)-oxo complex, [(N4Py)Mn-IV(O)](2+) (1), proceeds via one-step hydrogen-atom transfer (HAT) with a large deuterium kinetic isotope effect (KIE) of 3.2(3) at 293 K. In contrast, the same reaction with a triflic acid-bound manganese(IV)-oxo complex, [(N4Py)Mn-IV(O)](2+)-(HOTf)(2) (2), proceeds via electron transfer (ET) with no KIE at 293 K. Interestingly, when the reaction temperature is lowered to less than 263 K in the reaction of 2, however, the mechanism changes again from ET to HAT with a large KIE of 2.9(3). Such a switchover of the reaction mechanism from ET to HAT is shown to occur by changing only temperature in the boundary region between ET and HAT pathways when the driving force of ET from toluene derivatives to 2 is around -0.5 eV. The present results provide a valuable and general guide to predict a switchover of the reaction mechanism from ET to the others, including HAT.
DOI
10.1002/anie.201602460
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자연과학대학 > 화학·나노과학전공 > Journal papers
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