Mechanistic investigation of zwitterionic MOF-catalyzed enyne annulation using UNLPF-14-Mn^(Ⅲ) as catalyst  

作　　者：Taotao Liu Ruihong Duan Yanyan Wang Shijun Li Lingbo Qu Jinshuai Song Qiang Liu Yu Lan 

机构地区：[1]Green Catalysis Center,and College of Chemistry,Zhengzhou University,Zhengzhou 450001,China [2]Center of Basic Molecular Science(CBMS),Department of Chemistry,Tsinghua University,Beijing 100084,China [3]College of Chemistry and Chemical Engineering,Henan Institute of Science and Technology,Xinxiang 453000,China [4]School of Chemistry and Chemical Engineering,and Chongqing Key Laboratory of Theoretical and Computational Chemistry,Chongqing University,Chongqing 400030,China

出　　处：《Chinese Chemical Letters》2022年第9期4281-4286,共6页中国化学快报（英文版）

基　　金：supported by the National Natural Science Foundation of China (Nos. 21822303 21772020 22173083);Program for Science Technology Innovation Talents in Universities of Henan Province (No. 20HASTIT004);the support from the Henan Province Supercomputing Center

摘　　要：Hybrid quantum mechanics/molecular mechanics calculations were performed to elucidate how[Mn^(Ⅲ)porphyrin]^(+X−)-based metal-organic frameworks(MOFs)catalyze the[2+1]cycloisomerization of enynes and why zwitterionic MOFs exhibit strong activity in Lewis acid catalysis.The calculations showed that zwitterionic MOFs have a“pure cationic active center”leading to a concerted nucleophilic attack pathway with lower barriers.In contrast,metals with coordinating anions have reduced electrophilicity,resulting in a stepwise radical-type pathway with much higher barriers.Further calculations showed the nature of catalysis was strongly depended on the charge on the anion ligand.A good linear relationship between the NPA charge and barrier was found,and verified by 73 anions with small derivations,which presents a universal adaptive character for various coordinated anions.

关 键 词：ONIOM QM/MM Zwitterionic MOF [Mn^(III)porphyrin]^(+X−) Enyne annulation Mechanism Anion effect 

分 类 号：O621.251[理学—有机化学]