计算化学模拟法对制备乙硼烷和甲硅烷反应类型的研究

Computational Simulation Study on Type of Reaction for the Preparation of Diborane and Silane

采用计算化学模拟方法,在MP2/6-311+g(d)、HF/6-311+g(d)水平上考察了BCl_(3)、B_(2)H_(6)、LiCl、LiAlH_(4)、AlCl_(3)、SiCl_(4)、SiH_(4)中的Mulliken电荷、自然布局分析电荷(NPA电荷)、Hirshfeld布局电荷、原子偶极矩校正的Hirshfeld布局电荷(ADCH电荷),并对它们进行了拓扑结构分析,从而确定了各化合物中原子的氧化数。模拟结果表明,反应4BCl_(3)+LiAlH_(4)=2B_(2)H_(6)+3LiCl+3AlCl_(3)可以视为氧化还原反应,而反应SiCl_(4)+LiAlH_(4)=SiH_(4)+LiCl+AlCl_(3)是取代反应。

The Mulliken charge,natural population analysis,Hirshfeld population analysis,and atomic dipole moment corrected Hirshfeld population of BCl_(3),B_(2)H_(6),LiCl,LiAlH_(4),AlCl_(3),SiCl_(4)and SiH_(4)were examined by calculation quantum chemistry at the MP2/6-311+g(d),HF/6-311+g(d)level,and the topological analyses were performed,so the oxidation number of atoms in each compound was determined.The calculated results show that the reaction of 4BCl_(3)+LiAlH_(4)=2B_(2)H_(6)+3LiCl+3AlCl_(3)can be regarded as redox reaction,while the reaction ofSiCl_(4)+LiAlH_(4)=SiH_(4)+LiCl+AlCl_(3)is substitution reaction.