Acta Chimica Sinica ›› 2012, Vol. 70 ›› Issue (12): 1337-1346.DOI: 10.6023/A1112302

Special Topic

### OsO+氧化活化氢分子气相反应机理的密度泛函理论计算

1. 有机功能分子合成与应用教育部重点实验室 湖北大学化学化工学院 武汉 430062
• 投稿日期:2011-12-30 修回日期:2012-05-04 发布日期:2012-05-10
• 通讯作者: 张干兵 E-mail:gbzhang@yahoo.cn
• 基金资助:

固体表面物理化学国家重点实验室(厦门大学)开放基金资助项目.

### Density functional investigation on the Reaction Mechanisms of Oxidative Activation of Dihydrogen by Osmium Oxide Cation in Gas Phase

Liu Qiong, Wang Pei, Zhang Ganbing

1. The MOE Key Laboratory for the Synthesis and Application of Organic Functional Molecules, College of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062, China
• Received:2011-12-30 Revised:2012-05-04 Published:2012-05-10
• Supported by:

This project was supported by the State Key Laboratory of Physical Chemistry of Solid Surfaces at Xiamen University.

Density functional calculations with UB3LYP functional and an extended ECP basis set are employed to Calculate the geometries and energies for all possible reactants, intermediates, transition states and products on sextet, quartet and doublet surfaces in four pathways of addition (oxidative addition and [2+2]cycloaddition)-elimination, abstraction-rebound and oxene-insertion for investigating the mechanisms of oxidative activation of dihydrogen by osmium oxide cation. From the results calculated, the titled reaction is spin-forbidden, which starts on the quartet surface and ends on sextet surface, the overall reaction is exothermic by 21.0 kJ·mol-1. Oxene-insertion process is unfavorable thermodynamically due to more positive Gibbs free energy for the reactant complexes. The other three mechanisms proposed exhibit multiple-state-reactivity (MSR) or two-state-reactivity (TSR). Individually the surfaces in three spin states for the two addition-elimination pathways may cross over three times, while the sextet and quartet surfaces for abstraction-rebound may cross once, respectively. The abstraction-rebound mechanism starts on the H-abstraction process with uphill potential surfaces and high endothermicity, followed by a barrierless and highly exothermic rebound of H atom, thus it cannot take place at normal temperature. While the two addition-elimination processes have the same rate-determining step, where each barrier is about 156.9 kJ·mol-1,which is a little higher than that for the usual reactions in liquid, however it is possible to take place due to coupling with the highly exothermic steps before. Furthermore, the concerted [2+2] cycloaddition step has a lower barrier of only 28.7 kJ·mol-1, which is 113.7 kJ·mol-1 lower than that for the step of the reductive elimination of the first hydride in oxidative addition-elimination process. Thus, [2+2] cycloaddition process is more favorable than oxidative addition process kinetically.