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Density Functional Theory Calculations on Ni-Ligand Bond Dissociation Enthalpies
Bing Wang,Yao Fu,Hai-zhu Yu*,Jing Shi*
Author NameAffiliationE-mail
Bing Wang Department of Chemistry, University of Science and Technology of China, Hefei 230026, China  
Yao Fu Department of Chemistry, University of Science and Technology of China, Hefei 230026, China  
Hai-zhu Yu* Department of Polymer Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China yuhz@ustb.edu.cn 
Jing Shi* Department of Chemistry, University of Science and Technology of China, Hefei 230026, China shijing@ustc.edu.cn 
Abstract:
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 diffierent DFT functionals (such as B3LYP, M06, MPWB1K, etc.) and diffierent 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.
Key words:  Density functional theory, Ni complex, Bond dissociation enthalpy
FundProject:
镍-配体键解离焓的密度泛函理论研究
王冰,傅尧,于海珠*,石景*
摘要:
许多镍催化反应中包含镍与配体(如氮杂环卡宾、三级膦等)配位键的断裂与生成过程,准确计算Ni-L键解离焓有助于理解这类反应.以近期Nolan小组报道的Ni-L键的解离焓为基准,评估不同密度泛函理论(包括B3LYP、M06、MPWB1K等)、不同基组(包括Ni上的赝势基组和其它原子上的全电子基组)的计算准确性,发现MPWB1K/LanL2DZ:6-31+G(d,p)//MPWB1K/LanL2DZ:6-31G(d)方法得出的结果与实验值吻合度最佳,溶剂化效应的相关计算表明CPCM和PCM溶剂化模型表现良好.
关键词:  密度泛函理论,镍配合物,键解离焓
DOI:10.1063/1674-0068/27/06/640-646
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