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Adjacent Lone Pair (ALP) Effect: A Computational Approach for Its Origin by Huaiyu Zhang; Wei Wu; Basil M. Ahmed; Gellert Mezei; Yirong Mo is a Chemistry article available to read on EtoBox.

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The adjacent lone pair (ALP) effect is an experimental phenomenon in certain nitrogenous heterocyclic systems exhibitingt he preference of the products with lone pairs separated over other isomers with lone pairs adjacent. At heoretical elucidation of the ALP effect requires the decompositiono fi ntramolecular energy terms and the isolation of lone pair-lone pair interactions. Here we used the block-localized wavefunction (BLW) method within the ab initio valence bond (VB) theory to derive the strictly localized orbitals whicha re used to accommodate one-atom centered lone pairs and two-atom centered s or p bonds. As such, in-teractions among electron pairs can be directly derived. Two-electroni ntegrals between adjacent lone pairs do not support the view that the lone pair-lone pair repulsion is responsiblef or the ALP effect. Instead, the disabling of p conjugation greatly diminishes the ALP effect, indicating that the reduction of p conjugation in deprotonated forms with two s lone pairs adjacent is one of the major causes for the ALP effect. Further electrostatic potential analysis and intramolecular energy decompositionc onfirmt hat the other key factor is the favorable electr

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Author

Huaiyu Zhang; Wei Wu; Basil M. Ahmed; Gellert Mezei; Yirong Mo

Published

2016

Language

EN

Field

Chemistry (Physical Sciences)