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Deuterium kinetic isotope effects as redox mechanistic criterions
- Title
- Deuterium kinetic isotope effects as redox mechanistic criterions
- Authors
- Fukuzumi, Shunichi; Lee, Yong-Min; Nam, Wonwoo
- Ewha Authors
- 남원우; Shunichi Fukuzumi; 이용민
- SCOPUS Author ID
- 남원우
; Shunichi Fukuzumi![scopus](/images/layout/icon2.png)
; 이용민![scopus](/images/layout/icon2.png)
![scopus](/images/layout/icon2.png)
![scopus](/images/layout/icon2.png)
- Issue Date
- 2021
- Journal Title
- BULLETIN OF THE KOREAN CHEMICAL SOCIETY
- ISSN
- 0253-2964
1229-5949
- Citation
- BULLETIN OF THE KOREAN CHEMICAL SOCIETY vol. 42, no. 12, pp. 1558 - 1568
- Keywords
- acid-promoted electron transfer; deuterium kinetic isotope effect; inverse kinetic isotope effect; proton-coupled electron transfer; tunneling effect
- Publisher
- WILEY-V C H VERLAG GMBH
- Indexed
- SCIE; SCOPUS
![scopus](/images/layout/scopus2.gif)
- Document Type
- Article
- Abstract
- This account article focuses on deuterium kinetic isotope effects (KIEs) used as criterions to elucidate redox mechanisms including proton-, hydrogen- and hydride-transfer reactions. Hydrogen atom transfer (HAT) is composed of two elementary steps: electron transfer (ET) and proton transfer (PT), while hydride transfer is composed of three elementary steps: ET, PT, and ET. Large tunneling effects are often observed for proton-coupled electron-transfer (PCET) reactions of metal-oxygen complexes in which ET occurs to the metal center and PT occurs simultaneously to the ligand, exhibiting large KIEs. Whether HAT proceeds via sequential ET/PT, PT/ET, or concerted PCET (cPCET) depending on the redox properties of hydrogen donors and acceptors to exhibit different KIEs. Whether hydride transfer also proceeds via sequential ET/PT/ET, PT/ET/ET, or cPCET/ET depending on the redox properties of hydride donors and acceptors to exhibit different KIEs. Temperature dependence of KIEs for aldehyde deformylation reactions has enabled to distinguish two reaction pathways: one is a HAT and the other is a nucleophilic addition. The change of the mechanism from cPCET to sequential ET/PT is made possible by binding acids to the hydrogen and hydride acceptors when no KIE is observed. Inverse KIEs are also discussed for acid (or deuteron)-promoted ET reactions.
- DOI
- 10.1002/bkcs.12417
- Appears in Collections:
- 자연과학대학 > 화학·나노과학전공 > Journal papers
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