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Role of charge‐transfer effects in regioselectivity
Author(s) -
Korchowiec Jacek
Publication year - 2004
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.20328
Subject(s) - regioselectivity , charge (physics) , chemistry , molecule , computational chemistry , quantum , interaction energy , chemical physics , structural isomer , quantum chemistry , physics , stereochemistry , organic chemistry , quantum mechanics , catalysis , supramolecular chemistry
Abstract The energy‐partitioning scheme was used to study the regioselectivity problem. As a model system, Diels–Adler (DA) reaction was considered. It is shown that charge‐transfer (CT) energy is not responsible for experimentally observed trends in regioselectivity. However, it is the only contribution to the overall interaction energy that depends regularly on the type of substituents attached to reactant molecules. The main factors governing the orientation in DA reaction are deformation and Heitler–London energies. We have also demonstrated that the clear relationship between CT energy and the amount of charge transferred from one to another reactant exists for reactive systems that differ only in the substitution pattern. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005