关于HSCH(O)⇌(S)CHOH和HSNO⇌SNOH反应中氢转移的机制

On the mechanism of hydrogen transfer in the HSCH(O) <--> (S)CHOH and HSNO <--> SNOH reactions.

作者信息

Gutiérrez-Oliva Soledad, Herrera Bárbara, Toro-Labbé Alejandro, Chermette Henry

机构信息

Centro de Bioinformatica y Simulación Molecular, Universidad de Talca, Casilla 721, Talca, Chile.

出版信息

J Phys Chem A. 2005 Mar 3;109(8):1748-51. doi: 10.1021/jp0452756.

DOI:10.1021/jp0452756

PMID:16833500

Abstract

The 1,3-intramolecular hydrogen transfer in the HSCH(O) <--> (S)CHOH and HSNO <--> SNOH reactions is studied through density functional theory calculations. The reaction force together with structural and electronic properties is monitored along the reaction path to characterize the mechanism of hydrogen transfer. It is found that in both reactions the hydrogen transfer is activated by the structural rearrangement of the backbone atoms that allow the electrostatic interactions to promote the hydrogen transfer in a stepwise mechanism.

摘要

通过密度泛函理论计算研究了HSCH(O)⇌(S)CHOH和HSNO⇌SNOH反应中的1,3-分子内氢转移。沿着反应路径监测反应力以及结构和电子性质，以表征氢转移的机理。结果发现，在这两个反应中，氢转移都是由主链原子的结构重排激活的，这种重排使得静电相互作用以逐步机理促进氢转移。