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

Autor:	Hajime Hirao, Pratanphorn Chuanprasit
Rok vydání:	2015
Předmět:	Electron transfer Chemistry Computational chemistry Dimethylhydrazine General Physics and Astronomy Substrate (chemistry) Valence bond theory Density functional theory Physical and Theoretical Chemistry Proton-coupled electron transfer Photochemistry Bond-dissociation energy Homolysis
Zdroj:	Chemical Physics Letters. 621:188-192
ISSN:	0009-2614
Popis:	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.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::5afbfbe23e6b61f4eb57bb8dcf2b23de https://doi.org/10.1016/j.cplett.2014.12.027 Zobrazit plný text záznamu Full Text from ScienceDirect