title: Electronic forces as descriptors of nucleophilic and electrophilic regioselectivity and stereoselectivity.
abstract: One of the main tasks of theoretical chemistry is to rationalize computational results with chemical insights. Key concepts of such nature include nucleophilicity, electrophilicity, regioselectivity, and stereoselectivity. While computational tools are available to predict barrier heights and other reactivity properties with acceptable accuracy, a conceptual framework to appreciate above quantities is still lacking. In this work, we introduce the electronic force as the fundamental driving force of chemical processes to understand and predict molecular reactivity. It has three components but only two are independent. These forces, electrostatic and steric, can be employed as reliable descriptors for nucleophilic and electrophilic regioselectivity and stereoselectivity. The advantages of using these forces to evaluate molecular reactivity are that electrophilic and nucleophilic attacks are featured by distinct characteristics in the electrostatic force and no knowledge of quantum effects included in the kinetic and exchange-correlation energies is required. Examples are provided to highlight the validity and general applicability of these reactivity descriptors. Possible applications in ambident reactivity, σ and π holes, frustrated Lewis pairs, and stereoselective reactions are also included in this work.
authors.affiliation: Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China), Synergetic Innovation Center for Quantum Effects and Applications (SICQEA), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081, China and Research Computing Center, University of North Carolina, Chapel Hill, North Carolina 27599-3420, USA. shubin@email.unc.edu.
authors.forename: Shubin
authors.identifier: http://orcid.org/0000-0001-9331-0427
authors.initials: S
authors.lastname: Liu
authors.affiliation: Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China), Synergetic Innovation Center for Quantum Effects and Applications (SICQEA), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081, China.
authors.forename: Chunying
authors.initials: C
authors.lastname: Rong
authors.affiliation: Beijing Kein Research Center for Natural Sciences, Beijing 100022, P. R. China and Beijing Quanton Technology Co. Ltd., Beijing 100024, P. R. China.
authors.forename: Tian
authors.initials: T
authors.lastname: Lu