An attempt to evaluate the effect of proton-coupled electron transfer on the H-abstraction step of the reaction between 1,1-dimethylhydrazine and cytochrome P450 compound I

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Author(s)

Detail(s)

Original languageEnglish
Pages (from-to)188-192
Journal / PublicationChemical Physics Letters
Volume621
Publication statusPublished - 4 Feb 2015
Externally publishedYes

Abstract

A series of density functional theory and G4 calculations are performed to quantify the extent to which proton-coupled electron transfer (PCET) lowers the barrier for H-abstraction in the reaction between 1,1-dimethylhydrazine (UDMH) and the compound I intermediate of a cytochrome P450 enzyme. The homolytic bond dissociation energy of UDMH is larger than that of 1,4-cyclohexadiene; nevertheless, the H-abstraction barrier is significantly lower for the former substrate. The barrier lowering in the UDMH reaction caused by PCET is roughly estimated to be 9 kcal/mol. Valence bond structures are analyzed in detail to figure out how PCET lowers the barrier height.

Citation Format(s)

An attempt to evaluate the effect of proton-coupled electron transfer on the H-abstraction step of the reaction between 1,1-dimethylhydrazine and cytochrome P450 compound I. / Hirao, Hajime; Chuanprasit, Pratanphorn.

In: Chemical Physics Letters, Vol. 621, 04.02.2015, p. 188-192.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review