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 Sujuan Zheng;Heng Zhang;Qian Peng

作者机构：State Key Laboratory of Elemento-Organic ChemistryTianjin Key Laboratory of Biosensing and Molecular RecognitionFrontiers Science Center for New Organic MatterCollege of ChemistryNankai UniversityTianjin 300071China Haihe Laboratory of Sustainable Chemical TransformationTianjin 300192China 

出 版 物：《中国化学快报:英文版》 (Chinese Chemical Letters)

年 卷 期：2023年第34卷第8期

页      面：147-152页

核心收录：

学科分类：08[工学] 0805[工学-材料科学与工程（可授工学、理学学位）] 080502[工学-材料学] 0703[理学-化学] 

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. 

主　　题：Ni-Al bimetallic catalysis Secondary phosphine oxides Redox dehydrogenation Dual-SPO model 

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.