Ab Initio Calculation of M-H Bond Dissociation Energies of Cr-Group Metal Hydrides

doi:10.6023/A12070460

Acta Chimica Sinica ›› 2012, Vol. 70 ›› Issue (18): 1923-1929.DOI: 10.6023/A12070460 Previous Articles Next Articles

Article

铬族金属氢化物中M-H 键键能的从头计算

唐诗雅, 傅尧, 郭庆祥

中国科学技术大学化学系合肥 230026

投稿日期:2012-07-23 发布日期:2012-08-16
通讯作者: 傅尧,郭庆祥
基金资助:
项目受国家自然科学基金(Nos. 20832004, 20972148), 中国科学院(KJCX2-EW-J02)和中央高校基本科研业务费资助. 计算工作在中国科大和上海超算中心完成.

Ab Initio Calculation of M-H Bond Dissociation Energies of Cr-Group Metal Hydrides

Tang Shiya, Fu Yao, Guo Qingxiang

Department of Chemistry, University of Science and Technology of China, Hefei 230026

Received:2012-07-23 Published:2012-08-16
Supported by:
Supporting information for this article is available free of charge via the Internet at http://sioc-journal.cn. Project supported by the National Natural Science Foundation of China (Nos. 20832004, 20972148), Chinese Academy of Science (KJCX2-EW-J02) and the Fundamental Research Funds for the Central Universities. Computations were performed at the Supercomputing Center of USTC and Shanghai.

1. Ab Initio Calculation of M-H Bond Dissociation Energies of Cr-Group Metal Hydrides.PDF(293KB)

Abstract

The metal-hydrogen M-H bond homolysis of the Cr-group metal hydrides is a key process in the radical cyclization reactions mediated by these compounds, which directly affects the catalytic efficiency and selectivity of the reactions. Accurate prediction of M-H BDEs (bond dissociation energies) using theoretical methods not only improves our understanding about the structures and properties of the Cr-group metal hydride based catalysts, but also provides important insights into design of new generations of catalysts for radical cyclization reactions. For this purpose, we have calculated the M-H BDEs with different density functional theory methods (including MPW1K, MPW1b95, MPW1PW91, PBE1PBE, B3P86, O3LYP, TPSSH, MPW1KCIS, and TPSS) and compared the theoretical predictions with 14 reliable experimental M-H BDE values recently reported for the Cr-group metal hydrides. It is found that the B3P86/lanl2dz+p method could accurately predict the M-H BDEs with a precision of 1.6 kcal/mol. Using the B3P86/lanl2dz+p method, we next studied the structure-property relationship for the M-H BDEs in Cr-group metal hydrides. As to the periodical trends, we found that the effects of the metals on the M-H BDEs are greater than the effects of the ligands. The M-H BDEs increase in the order:first row metal

Key words: transition-metal hydride, bond dissociation energy, ab initio calculation, hybridization defects

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Tang Shiya, Fu Yao, Guo Qingxiang. Ab Initio Calculation of M-H Bond Dissociation Energies of Cr-Group Metal Hydrides[J]. Acta Chimica Sinica, 2012, 70(18): 1923-1929.

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铬族金属氢化物中M-H 键键能的从头计算

Ab Initio Calculation of M-H Bond Dissociation Energies of Cr-Group Metal Hydrides

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