Overriding the inherent alkalinity to dual phosphinito bimetallic catalyst for C(sp^(2))-C(sp^(3))formation:A combined computational and experimental study  

作　　者：Sujuan Zheng Heng Zhang Qian Peng 

机构地区：[1]State Key Laboratory of Elemento-Organic Chemistry,Tianjin Key Laboratory of Biosensing and Molecular Recognition,Frontiers Science Center for New Organic Matter,College of Chemistry,Nankai University,Tianjin 300071,China [2]Haihe Laboratory of Sustainable Chemical Transformation,Tianjin 300192,China

出　　处：《Chinese Chemical Letters》2023年第8期147-152,共6页中国化学快报（英文版）

基　　金：We gratefully acknowledge the National Key Research and Development Program of China(No.2021YFA1500100);the National Natural Science Foundation of China(Nos.92156017,21890722,22188101);the NSF of Tianjin Municipality(No.19JCJQJC62300);Tianjin Research Innovation Project for Postgraduate Students(No.2019YJSB081);Haihe Laboratory of Sustainable Chemical Transformation of Tianjin for generous financial support.

摘　　要：Unraveling the catalytic reaction mechanism is a long-term challenge for developing efficient catalysts.The blooming bimetallic catalyst have enabled to activate inert bonds and realize complex C-C formation.Herein,we theoretically discover a dual-phosphinito bridged hetero-bimetallic species that verified by NMR experiments.Our results indicate only dual-phosphinito Ni-Al model can be an active catalyst in asymmetric cycloadditions via C-C activation and C-H activation,which can well rationalize the experimental observations for both reactivity and stereo-selectivity.An unprecedented tandem redox dehydrogenation mechanism was revealed to control the formation of this active species overriding the inherent basicity.Synergistic Lewis acid and eg orbital interactions,including dz2 orbital reoccupation and d_(x^(2)−y^(2))orbital recombination,were disclosed to understand both thermodynamic and kinetic advance of dual-bridged model,displaying feasible redox properties.

关 键 词：Ni-Al bimetallic catalysis Secondary phosphine oxides Redox dehydrogenation Dual-SPO model 

分 类 号：TQ426[化学工程]