The application of aromaticity and antiaromaticity to reaction mechanisms  

作　　者：Qin Zhu Shuwen Chen Dandan Chen Lu Lin Kui Xiao Liang Zhao Miquel Solà Jun Zhu 

机构地区：[1]State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials(iChEM),College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China [2]Key Laboratory for Organic Electronics&Information Displays(KLOEID)and Institute of Advanced Materials(IAM),SICAM,Nanjing University of Posts&Telecommunications,Nanjing 210023,China [3]Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology(Ministry of Education),Department of Chemistry,Tsinghua University,Beijing 100084,China [4]Institute of Computational Chemistry and Catalysis and Department of Chemistry,University of Girona,C/M.Aurèlia Capmany,69,17003 Girona,Catalonia,Spain [5]School of Science and Engineering,The Chinese University of Hong Kong,Shenzhen 518172,China

出　　处：《Fundamental Research》2023年第6期926-938,共13页自然科学基础研究（英文版）

基　　金：the National Natural Science Foundation of China(22073079,22025105 and 21873079);the Ministry of Education of China(H20200504);the Top-Notch Young Talents Program of China is gratefully acknowledged;M.S.thanks the Ministerio de Ciencia e Innovación of Spain(project PID2020-113711GB-I00);the Generalitat de Catalunya(project 2017SGR39).

摘　　要：Aromaticity,in general,can promote a given reaction by stabilizing a transition state or a product via a mobility ofπelectrons in a cyclic structure.Similarly,such a promotion could be also achieved by destabilizing an antiaromatic reactant.However,both aromaticity and transition states cannot be directly measured in experiment.Thus,computational chemistry has been becoming a key tool to understand the aromaticity-driven reaction mechanisms.In this review,we will analyze the relationship between aromaticity and reaction mechanism to highlight the importance of density functional theory calculations and present it according to an approach via either aromatizing a transition state/product or destabilizing a reactant by antiaromaticity.Specifically,we will start with a particularly challenging example of dinitrogen activation followed by other small-molecule activation,Csingle bondF bond activation,rearrangement,as well as metathesis reactions.In addition,antiaromaticity-promoted dihydrogen activation,CO_(2)capture,and oxygen reduction reactions will be also briefly discussed.Finally,caution must be cast as the magnitude of the aromaticity in the transition states is not particularly high in most cases.Thus,a proof of an adequate electron delocalization rather than a complete ring current is recommended to support the relatively weak aromaticity in these transition states.

关 键 词：AROMATICITY ANTIAROMATICITY Reaction mechanism Frustrated Lewis pairs Dinitrogen activation Small molecule activation 

分 类 号：O62[理学—有机化学]