Theoretical Studies on the Dihydrogen Bonding Between Shortchain Hydrocarbon and Magnesium Hydride

作     者：LI Li BAI Fuquan ZHANG Hongxing 

作者机构：State Key Laboratory of Theoretical and Computational Chemistry Institute of Theoretical Chemistry Jilin University Changchun 130021 P. R. China 

出 版 物：《Chemical Research in Chinese Universities》 (高等学校化学研究（英文版）)

年 卷 期：2014年第30卷第5期

页      面：831-836页

核心收录：

学科分类：1007[医学-药学(可授医学、理学学位)] 07[理学] 070203[理学-原子与分子物理] 0703[理学-化学] 0702[理学-物理学] 10[医学] 

基　　金：Supported by the National Natural Science Foundation of China(Nos.21003057  21173096)  the National Basic Research Program of China(No.2013CB834801) and the Specialized Research Fund for the Doctoral Program of Higher Education of China(No.20110061110018) 

主　　题：Dihydrogen bond Atom in molecule(AIM) theory Bond critical point Natural bond orbital(NBO) Chargetransfer 

摘      要：The C--H…H dihydrogen-bonded complexes of methane, ethylene, acetylene, and their derivatives with magnesium hydride were systematically investigated at MP2/aug-cc-PVTZ level. The results confirm that the strength of dihydrogen bonding increases in the following order of proton donors： C（sp3）-H〈C（sp2）-H〈C（sp）-H and chlorine substituents enhance the C-H…H interaction. In the majority of the complexes with a cyclic structure, the Mg-H proton-accepting bond is more sensitive to the surroundings than C-H proton-donating bond. The nature of the electrostatic interaction in these C-H…H dihydrogen bonds was also unveiled by means of the atoms in mo- lecules（AIM） analysis. The natural bond orbital（NBO） analysis suggests that the charge transfer in the cyclic com- plexes is characteristic of dual-channel. The direction of the net charge transfer in the cyclic complexes is contrary to that previously found in dihydrogen bonded systems.