Insight into the Detailed Mechanism of HRh(CO)(PPh_3)_3 Catalyzed Hydroformylation of 1-Phenyl-1-(3-pyridyl)ethene:A DFT Study  

作　　者：罗小玲 梁国明 李荣 孙宇阳 

机构地区：[1]Key Laboratory of Functional Material,Chongqing Normal University

出　　处：《Chinese Journal of Structural Chemistry》2010年第5期789-795,共7页结构化学（英文）

基　　金：Supported by the Education Commission of Chongqing (kj070809);Chongqing Normal University (06XLY018);crosswise project of Sichuan Normal University

摘　　要：Density functional calculations have been used to study the mechanism of 1-phenyl-1-（3-pyridyl）ethene hydroformylation using rhodium catalyst.Our calculations reveal that the rate-determining step is the oxidative addition of hydrogen molecule and the preferred path is the one involving ts3ans for the lowest activation free-energy （ΔrGa）,63.8 kJ/mol.This reaction is demonstrated to be strong exothermic by-96.6 kJ/mol of branched products and-98.2 kJ/mol of linear products.And the predominant product is the linear 3-phenyl-3-（3-pyridal）propanal （pr-ns） determined by both thermodynamics and kinetics.These results are in agreement with the practicality experimental studies.Density functional calculations have been used to study the mechanism of 1-phenyl-1-（3-pyridyl）ethene hydroformylation using rhodium catalyst.Our calculations reveal that the rate-determining step is the oxidative addition of hydrogen molecule and the preferred path is the one involving ts3ans for the lowest activation free-energy （ΔrGa）,63.8 kJ/mol.This reaction is demonstrated to be strong exothermic by-96.6 kJ/mol of branched products and-98.2 kJ/mol of linear products.And the predominant product is the linear 3-phenyl-3-（3-pyridal）propanal （pr-ns） determined by both thermodynamics and kinetics.These results are in agreement with the practicality experimental studies.

关 键 词：HYDROFORMYLATION 1-phenyl-1-（3-pyridyl）ethane Rh catalyst regioselectivity B3LYP 

分 类 号：O621.13[理学—有机化学]