Mechanism of the Ir/Pd catalyzed photocarboxylation of aryl halides  

作　　者：Ying Lv Bing Wang Haizhu Yu 

机构地区：[1]Department of Chemistry and Centre for Atomic Engineering of Advanced Materials,Anhui University.Hefei 230601,China [2]Department of Chemistry,University of Science and Technology of China,Hefei 230026,China

出　　处：《Chinese Chemical Letters》2021年第4期1403-1406,共4页中国化学快报（英文版）

基　　金：the financial support from the National Natural Science Foundation of China(Nos.21672001,51961135104);the technical support of high-performance computing platform of Anhui University。

摘　　要：The recent Ir/Pd co-catalyzed photo carboxylation of aromatic halides with CO_(2) has shown high efficiency and excellent functional group tolerance for preparing aromatic carboxylic acids and esters.With the aid of density functional theory(DFT)calculations,the carboxylation starts with two parallel steps,i.e.,oxidative addition of aromatic halides on Pd~0 and reductive quenching of the photocatalyst Ir(ppy)_(2)(dtbpy)~+with amine.Thereafter,a successive oxidation of Pd~Ⅱwith the amine radical(generated by the reaction of cationic radical amine and Cs_(2) CO_(3)and Ir~Ⅱspecies occurs to generate Pd~0,from which the carboxylation occurs easily via a coordination,Pd-C insertion step.The release of the carboxylate product then regenerates the catalyst.

关 键 词：CARBOXYLATION PD-CATALYSIS DFT Charge state MECHANISM 

分 类 号：O621.251[理学—有机化学]