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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, Jieun; Kim, Surin; Lee, Yong-Min; Nam, Wonwoo; Fukuzumi, Shunichi
- Ewha Authors
- 남원우; Shunichi Fukuzumi; 이용민; 정지은
- SCOPUS Author ID
- 남원우; Shunichi Fukuzumi; 이용민; 정지은
- Issue Date
- 2016
- Journal Title
- ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
- ISSN
- 1433-7851
1521-3773
- Citation
- ANGEWANDTE CHEMIE-INTERNATIONAL EDITION vol. 55, no. 26, pp. 7450 - 7454
- Keywords
- bioinorganic chemistry; electron transfer; hydrogen atom transfer; manganese(IV)-oxo complex; mechanism switchover
- Publisher
- WILEY-V C H VERLAG GMBH
- Indexed
- SCIE; SCOPUS
- Document Type
- Article
- 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
- Appears in Collections:
- 자연과학대학 > 화학·나노과학전공 > Journal papers
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