Quantitative approach to evaluate the intramolecular interaction of the appointed and unlinked groups or nonhydrogen atoms within organic compounds

摘要

This paper reported a new approach to quantitatively evaluate the interaction of the appointed and indirectly linked groups or nonhydrogen atoms in molecules by designing unique isodesmic reactions, calculating their energy changes, and getting so-called interaction energy (E-i). The consistency of the sign and amount of E-i with the common qualitative descriptions on some intramolecular effects confirmed the validity of the new method. Two applications of this method to halogenated methane and ethane, and nitro compounds showed: (1) for any group of molecules with the same skeleton, E-i of all substitution groups or nonhydrogen atoms can be used to compare their molecular stabilities; (2) for the appointed groups in different molecules, E-i of them can reveal the nature (attraction or repulsion) and the strength of their interaction. All these indicated that E-i is a useful tool to reflect the intramolecular interaction of appointed and unlinked groups or nonhydrogen atoms. Copyright (C) 2008 John Wiley & Sons, Ltd.