Uncatalyzed 1,4-hydrogenation of polycyclic aromatic hydrocarbons: A computational study

被引：10

作者：

Zhong, George

Chan, Bun ^{[1
]}

Radom, Leo

机构：

[1] Univ Sydney, Sch Chem, Sydney, NSW 2006, Australia

[2] Univ Sydney, Ctr Excellence Free Rad Chem & Biotechnol, Sydney, NSW 2006, Australia

来源：

JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM | 2007年 / 811卷 / 1-3期

基金：

澳大利亚研究理事会;

关键词：

density functional theory calculations; hydrogenation; polycyclic aromatic hydrocarbons; Hammond postulate; Bell-Evans-Polanyi principle;

D O I：

10.1016/j.theochem.2007.02.030

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Quantum chemistry calculations have been used to study the 1,4-hydrogenation reactions of selected polycyclic aromatic hydrocarbons. We find that the geometric parameters associated with the transition structures are consistent with the Hammond postulate. In addition, the hydrogenation barriers vary linearly with the reaction energy, consistent with the Bell-Evans-Polanyi (BEP) principle. The regiochemistry for the hydrogenation of polycyclic aromatic hydrocarbons may be broadly predicted by examining the extent of disruption to aromaticity for the various possible hydrogenation pathways, or in finer detail by utilizing the BEP relationship. (c) 2007 Elsevier B.V. All rights reserved.

引用

页码：13 / 17

页数：5

共 33 条

[1] NICKEL HYDROGENASES - IN SEARCH OF THE ACTIVE-SITE [J].