镍辅助丙醛在气相中C-C和C-H键活化的理论研究

Zhao Pei-Pei, Wang Yong-Cheng, Sheng Yang, Jia Yi-Ming

College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu 730070, PR China.

Comput Theor Chem. 2017 Aug 15;1114:140-145. doi: 10.1016/j.comptc.2017.05.030.

The reactions of Ni with propionaldehyde in the gas phase have been systematically investigated using density functional theory at the B3LYP/def2-TZVP level. The decomposition reaction mechanism has been identified. Our calculations indicated that Ni can assist decomposition of propionaldehyde to form NiCO and CH through two types of reaction channel: C-C bond activation and C-H bond activation. In addition, charge decomposition analysis (CDA) was carried out to obtain a deeper understanding for orbital interaction of the initial complex. The bonding properties of the species involved were discussed by means of diverse analysis methods including electron localization function (ELF) and atoms in molecules (AIM).

采用密度泛函理论在B3LYP/def2-TZVP水平上系统研究了镍与丙醛在气相中的反应。确定了分解反应机理。我们的计算表明，镍可通过两种反应通道协助丙醛分解形成NiCO和CH：C-C键活化和C-H键活化。此外，进行了电荷分解分析（CDA）以更深入地了解初始络合物的轨道相互作用。通过包括电子定域函数（ELF）和分子中的原子（AIM）在内的多种分析方法讨论了所涉及物种的键合性质。