Cationic quaternary ammonium-stabilized Nb oxoclusters catalyze reductive amination of carbon dioxide with hydrosilane

作     者：Yuan Ma Xinjian Wei Jian Fang Qingpo Peng Wen Xu Zhenshan Hou Yuan Ma;Xinjian Wei;Jian Fang;Qingpo Peng;Wen Xu;Zhenshan Hou

作者机构：Key Laboratory for Advanced MaterialsResearch Institute of Industrial CatalysisSchool of Chemistry and Molecular EngineeringEast China University of Science and TechnologyShanghai200237China 

出 版 物：《Green Chemical Engineering》 (绿色化学工程（英文）)

年 卷 期：2022年第3卷第2期

页      面：146-156页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 0817[工学-化学工程与技术] 08[工学] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：The authors are grateful for financial support from the National Natural Science Foundation of China(21773061 21978095) 

主　　题：CO_(2) Amine Hydrosilane N-formylation Polyoxoniobate 

摘      要：The N-formylation of amines with CO_(2)and hydrosilanes is an emerging yet important reaction in fine chemical ***,we have reported a methyltrioctylammonium cation(TOMA)stabilized Nb oxocluster catalyst that can effectively realize two electron reduction of CO_(2)and form C-N bond simultaneously,leading to the corresponding *** oxocluster catalyst exhibits excellent catalytic activity to transform secondary and primary amines into the corresponding formamides,with the conversion ranging from 81.5%to 99.2%under room temperature ***,the Nb oxocluster catalyst shows the unique characteristics of ionic liquids,and it is highly robust and easy to be recycled for five times with negligible loss of catalytic *** the basis of the activity tests and structure characterization of Nb catalysts,it was found that TOMA cation played an important role in modulating the Nb oxocluster with high stability and uniform *** mechanism studies demonstrate that the formylation reaction proceeds through the formation of silyl formate intermediate rather than carbamate,and the Lewis base site of negative oxygen atoms from polyoxoniobate anions can exert a favorable impact on activation both CO_(2)and Si-H bond of PhSiH 3,allowing that N-formylation reaction proceed smoothly under very mild reaction conditions.