Density Functional Theory Calculations on Ni-Ligand Bond Dissociation Enthalpies

作者：Wang Bing; Fu Yao; Yu Hai zhu^*; Shi Jing

来源：Chinese Journal of Chemical Physics, 2014, 27(6): 640-646.

DOI：10.1063/1674-0068/27/06/640-646

• Density functional theory
• Ni complex
• Bond dissociation enthalpy

The formation and breaking of Ni-L (L=N-heterocyclic carbene, tertiary phosphine etc.) bond is involved in many Ni-catalyzed/mediated reactions. The accurate prediction of Ni-L bond dissociation enthalpies (BDEs) is potentially important to understand these Ni-complex involving reactions. We assess the accuracy of different DFT functionals (such as B3LYP, M06, MPWB1K, etc.) and different basis sets, including both effective core potentials for Ni and the all electron basis sets for all other atoms in predicting the Ni-L BDE values reported recently by Nolan et al. [J. Am. Chem. Soc. 125, 10490 (2003) and Organometallics 27, 3181 (2008)]. It is found that the MPWB1K/LanL2DZ:6-31+G(d,p)//MPWB1K/LanL2DZ:6-31G(d) method gives the best correlations with the experimental results. Meanwhile, the solvent effect calculations (with CPCM, PCM, and SMD models) indicate that both CPCM and PCM perform well.

• 出版日期2014-12
• 单位北京科技大学; 中国科学技术大学