Ligand Size Effect on PdLn Oxidative Addition with Aryl Bromide: A DFT Study
doi: 10.1088/1674-0068/23/02/175-179
Funds:
This work was supported by the National Natural Sci-ence Foundation of China (No.20776089) and the New Century Excellent Talents Program of Ministry of Ed-ucation (No.NCET-05-0783). The State Key Labora-tory of Polymer Materials Engineering in Sichuan Uni-versity was acknowledged for providing dmol3 modules and Prof. Ying Xue, Xiang-yuan Li, and Quan Zhu were grateful for the useful discussions.
- Received Date: 2009-11-10
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Key words:
- Process simulation, Ligand size effect, Oxidative addition, Cross-coupling reaction, DFT method
Abstract: The process and mechanism of the ligand volume controlled Pd(PR3)2 (PR3=PH3, PMe3, and PtBu3) oxidative addition with aryl bromide were investigated, using density functional theory method with the conductor-like screening model. Association pathway and dissocia-tion pathway were investigated by the comparison of several energies. The cleavage energy of Pd(PR3)2 complex was calculated, as well as the oxidative addition reaction barrier energy of Pd(PR3)n (n=1,2) with aryl bromide in N,N-dimethylformamide solvent. This study proved that the ligands volume possessed a great impact on the mechanism of oxidative addition: less bulky ligand palladium associated with aryl bromide via two donor ligands,but larger bulky ligand palladium coordinated via monoligand.
| Citation: | Wen-jing Sun, Wei Chu, Liang-jun Yu, Cheng-fa Jiang. Ligand Size Effect on PdLn Oxidative Addition with Aryl Bromide: A DFT Study[J]. Chinese Journal of Chemical Physics , 2010, 23(2): 175-179. doi: 10.1088/1674-0068/23/02/175-179
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