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Ligand Size Effect on PdLn Oxidative Addition with Aryl Bromide: A DFT Study
Wen-jing Sun,Wei Chu*,Liang-jun Yu,Cheng-fa Jiang*
Author NameAffiliationE-mail
Wen-jing Sun Department of Chemical Engineering, Sichuan University, Chengdu 610065, China  
Wei Chu* Department of Chemical Engineering, Sichuan University, Chengdu 610065, China chuwei65@yahoo.com.cn 
Liang-jun Yu Hunan Zhongchuang Chemical Co. Ltd., Yueyang 414012, China  
Cheng-fa Jiang* Department of Chemical Engineering, Sichuan University, Chengdu 610065, China jiangcf1@yahoo.com 
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.
Key words:  Process simulation, Ligand size effect, Oxidative addition, Cross-coupling reaction, DFT method
FundProject:
Ligand Size Effect on PdLn Oxidative Addition with Aryl Bromide: A DFT Study
孙文晶,储伟*,余良军,江成发*
摘要:
采用密度泛函理论的COSMO模型模拟了在DMF溶剂中三种不同体积的钯配体Pd(PR3)n (n=1,2) (PR3=PH3, PMe3, PtBu3)与溴苯氧化加成的反应过程. 对比双配体Pd(PR3)2的裂解能以及双配体钯Pd(PR3)2和单配体钯Pd(PR3)氧化加成过程的能垒;结果表明,小体积的配体PH3和PMe3是以双配位的形式参加氧化加成过程的,而较大体积的配体PtBu3是以单配位钯的形式参加氧化加成过程的.
关键词:  配体体积效应,氧化加成,密度泛函理论方法,偶联反应,过程模拟
DOI:10.1088/1674-0068/23/02/175-179
分类号: