四川大学学报（自然科学版）2025，Vol.62Issue(3)：689-695,7.DOI:10.19907/j.0490-6756.240186
β-双烯酮亚胺Ga(Ⅲ)和Ge(Ⅳ)配合物活化Si-H键的理论研究
A theoretical study on Si-H bond activation using β-diketiminato ligated Ga(Ⅲ)and Ge(Ⅳ)complexes
摘要
Abstract
This study employs density functional theory(DFT)calculations to investigate the reaction mechanisms and activity differences in Si-H bond activation mediated by β-diketiminate(BDI)Ga(III)and Ge(IV)complexes.The calculations show that Si-H bond activation in both[(BDI)tBuGa]and[(BDI)Ge]complexes proceeds via a Lewis acid-Lewis base cooperation activation mechanism between central metal and ligand.The energy minimum reaction pathway for the Si-H bond activation with the[(BDI)Ge]complex in-volves the 1,5-concerted addition and intramolecular SiH3+cation transfer steps.The 1,5-concerted addition demands for the higher energy barrier(27.3 kcal·mol-1)is the rate-determining step(RDS)for the whole re-action pathway.The transition state of the intramolecular SiH3+cation transfer,with the relative Gibbs free energy of 36.7 kcal·mol-1 is the energy highest point on the potential energy surface(PES).Compared to the[(BDI)tBuGa]complex,Si-H bond activation using the[(BDI)Ge]complex requires the higher energy barrier,indicating the lower reactivity of the[(BDI)Ge]complex towards Si-H bond activation.Based on the results of the energy decomposition analysis and Extended Transition State-Natural Orbitals for Chemical Valence analysis,the lower reactivity of the[(BDI)Ge]complex in Si-H bond activation can be ascribed to the higher Pauli repulsion energy between the SiH4 molecule and[(BDI)Ge]fragments.关键词
β-双烯酮亚胺/受阻路易斯酸碱对/Si-H键活化Key words
β-diketiminates/Frustrated Lewis pairs/Si-H bond activation分类
化学引用本文复制引用
李彩琴,赵建国,曹秀丽,李唯一,刘荔贞,李小花..β-双烯酮亚胺Ga(Ⅲ)和Ge(Ⅳ)配合物活化Si-H键的理论研究[J].四川大学学报（自然科学版）,2025,62(3):689-695,7.基金项目
山西省高等学校科技创新项目(2021L399) （2021L399）
