View : 447 Download: 0
Acid-promoted hydride transfer from an NADH analogue to a Cr(iii)-superoxo complex via a proton-coupled hydrogen atom transfer
- Title
- Acid-promoted hydride transfer from an NADH analogue to a Cr(iii)-superoxo complex via a proton-coupled hydrogen atom transfer
- Authors
- Devi T.; Lee Y.-M.; Fukuzumi S.; Nam W.
- Ewha Authors
- 남원우; 이용민; Shunichi Fukuzumi
- SCOPUS Author ID
- 남원우; Shunichi Fukuzumi
- Issue Date
- 2021
- Journal Title
- Dalton Transactions
- ISSN
- 1477-9226
- Citation
- Dalton Transactions vol. 50, no. 2, pp. 675 - 680
- Publisher
- Royal Society of Chemistry
- Indexed
- SCIE; SCOPUS
- Document Type
- Article
- Abstract
- The sequential transfer of an electron, a proton and an electron in a hydride transfer from dihydronicotinamide adenine dinucleotide (NADH) and its analogues has never been separated well. In addition, the effect of acids on hydride transfer from an NADH analogue to a metal-superoxo species has yet to be reported. We report herein the first example of an acid-promoted hydride transfer from an NADH analogue, 10-methyl-9,10-dihydroacridine (AcrH2), to a Cr(iii)-superoxo complex, [(TMC)CrIII(O2)]2+, in the presence of HOTf in MeCN at 233 K. The acid-promoted hydride transfer from AcrH2 to [(TMC)CrIII(O2)]2+ occurs via a proton-coupled hydrogen atom transfer from AcrH2 to [(TMC)CrIII(O2)]2+ to produce a radical cation (AcrH2+) with an inverse deuterium isotope effect (KIE) of 0.93(5). AcrH2+ decayed via a proton transfer from AcrH2+ to AcrH2 with a KIE of 2.0(1), followed by the reaction of 10-methylacridinyl radical (AcrH) with [(TMC)CrIII(H2O2)]3+ to produce a 10-methylacridinium ion (AcrH+) and [(TMC)CrIII]3+. This work provides valuable insights into the mechanism of hydride transfer of NADH analogues by metal-superoxo intermediates, such as the switchover of the reaction mechanism from a one-step to a separated multi-step pathway in the presence of an acid. © 2021 The Royal Society of Chemistry.
- DOI
- 10.1039/d0dt04004e
- Appears in Collections:
- 자연과학대학 > 화학·나노과학전공 > Journal papers
- Files in This Item:
There are no files associated with this item.
- Export
- RIS (EndNote)
- XLS (Excel)
- XML