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Kinetic, thermodynamic and mechanistic studies on the reduction of carbenium ions by NAD(P)H analogues
Author(s) -
Cheng JinPei,
Lu Yun
Publication year - 1997
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/(sici)1099-1395(199707)10:7<577::aid-poc920>3.0.co;2-t
Subject(s) - chemistry , nad+ kinase , hydride , kinetic energy , ion , electron transfer , hydrogen atom , hydrogen atom abstraction , hydrogen , computational chemistry , one electron reduction , photochemistry , stereochemistry , enzyme , organic chemistry , physics , alkyl , electrode , quantum mechanics , electrochemistry
Hydride transfer mechanisms of the reductions of xanthylium ion by NAD(P)H analogues (i.e. BNAH, HEH and AcrH 2 ) were investigated. Both the kinetic observations and an analysis of thermodynamic driving forces for each mechanistic step in all the possible mechanisms indicate that the reductions are initiated by a rate‐determining electron transfer, followed by a fast hydrogen atom abstraction. The mechanism of the reductions of 9‐phenylxanthylium and triphenylmethylium ions by BNAH were also investigated and are similarly discussed. © 1997 John Wiley & Sons, Ltd.