Insight into generalized local softness based on ABEEM‐σπ method: Electrophilic additions to alkenes

According to the local hard‐soft acid – base (HSAB) principle, the generalized local softness has been investigated based on the electrophilic reactions of H2O, HF, HCl and HBr to alkenes, and the effect of the softness on the chemical reactivity was studied in terms of the ab initio and atom‐bond e...

Full description

Saved in:
Bibliographic Details
Published in:Journal of the Chinese Chemical Society (Taipei) 2022-02, Vol.69 (2), p.228-238
Main Authors: Ding, Yan‐Li, Sun, Chang‐Liang, Guo, Xiao‐Jiao, Mu, Ji‐Rong
Format: Article
Language:English
Subjects:
ABEEM‐σπ method
Alkenes
Chemical reactions
chemical reactivity
Electronegativity
Equalization
Finite difference method
generalized local softness
Investigations
Reactivity
Regioselectivity
Softness
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:According to the local hard‐soft acid – base (HSAB) principle, the generalized local softness has been investigated based on the electrophilic reactions of H2O, HF, HCl and HBr to alkenes, and the effect of the softness on the chemical reactivity was studied in terms of the ab initio and atom‐bond electronegativity equalization method plus σπ (ABEEM‐σπ) method. Studies show that the finite difference approximation with ab initio method cannot always be used to predict the regioselectivity of the investigated reactions in terms of the local HSAB principle. But ABEEM‐σπ model could well describe chemical reactivity according to the local HSAB principle. A significant characteristic of the ABEEM‐σπ method is that the double bond is explicitly considered and partitioned. The square sums of differences of the local softness of the reaction center atoms, that is, Δs, or ΔSG with the generalized local softness and ∆sχ with the electronegativity, have been studied on the considered electrophilic additions. Studies indicate that ΔSG can be utilized not only to predict regioselectivity rules but also to rationalize the chemical reactivity of these addition reactions, and the generalized local softness is more suitable for the investigation of chemical reactivity between two chemical species. The effect of the softness on the chemical reactivity was studied in terms of the electrophilic additions of H2O, HF, HCl and HBr to alkenes based on the local hard soft acid base principle. Studies indicate that ΔSG with the generalized local softness could not only explain the regioselectivity of the alkene reactions, but also rationalize the chemical reactivity.
ISSN:0009-4536
2192-6549
DOI:10.1002/jccs.202100392