| NCBBH…HNa(H2O)n和CNBBH…HNa(H2O)n(n=1~5)结构与性质的理论研究 |
| Theoretical Study on the Structures and Properties of NCBBH…HNa(H2O)n and CNBBH…HNa(H2O)n(n=1~5) |
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| 摘要: 为了探索缺电子B-H键作为质子供体形成双氢键复合物的溶剂化效应，分别采用DFT-B3LYP/6-311++G**和CCSD(T)/6-311++G**方法对NCBBH…HNa和CNBBH…HNa及其水合物NCBBH…HNa(H2O)n和CNBBH…HNa(H2O)n(n=1~5)进行了结构优化和相互作用能计算，并利用AIM (atom in molecule)方法分析了H…H键特征，借助前线分子轨道理论探讨了水合物中双氢键形成H-H共价键的本质。结果表明：随着H2O分子数的增加，B-H键拉长，H…H距离缩短，双氢键由离子型向共价型过渡；当H2O分子数达到4时，双氢键相互作用能和NCBBH…HNa与水分子间的相互作用能分别达到-374.21和-306.50 kJ·mol-1，形成了H-H共价键；缺电子B-H键作为质子供体形成双氢键复合物的水合物析出H2的能力比FH…HLi(H2O)n弱。 |
| 关键词: 双氢键复合物 缺电子B-H键 溶剂化效应 B3LYP CCSD(T) AIM |
| 基金项目: |
| Abstract: In this paper, our main aim is to examine the solvation effect on the dihydrogen-bonded complex in which the electron-deficient B-H group is as proton donor. NCBBH…HNa and CNBBH…HNa as well as their hydrated complexes NCBBH…HNa(H2O)n and CNBBH…HNa(H2O)n (n=1~5) have been fully optimized using DFT-B3LYP/6-311++G** method. The intermolecular interactions have been investigated at CCSD(T)/6-311++G** level. The topological electron charge density has been analyzed by AIM (atom in molecule) method to characterize the property of the H…H bond. The frontier molecular orbitals are presented in order to reveal the nature of the formation of the H-H covalent bonds in the hydrated complexes. The result shows that, with the increase of the number of surrounding water molecules, the B-H bond length is increased while the H…H distance is decreased accompanied by the conversion of the H…H bonding nature from the ionic bond to the covalent bond. When the number of the surrounding water molecules is up to 4, the dihydrogen-bonded interaction and that between the water molecules and NCB=BH…HNa are increased to -374.21 and -306.50 kJ·mol-1, respectively, and the H-H covalent bond is formed. The dehydrogenation reaction for the hydrated complexes of dihydrogen-bonded system involving the electron-deficient B-H group as proton donor might be more difficult than that for FH…HLi(H2O)n. |
| Keywords: dihydrogen-bonded complex electron-deficient B-H group solvation effect B3LYP CCSD(T) AIM |
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| 高 媛,张 琳,张德林,王 勇,姚爱琴.NCBBH…HNa(H2O)n和CNBBH…HNa(H2O)n(n=1~5)结构与性质的理论研究[J].无机化学学报,2012,28(4):679-685. |
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