Deprotonation of 1,2-dialkylpyridinium ions: a DFT study of reactivity and site selectivity

Gupta, Neelima ; Garg, Reena ; Shah, Kirti Kr. ; Tanwar, Akhilesh ; Pal, Sourav (2007) Deprotonation of 1,2-dialkylpyridinium ions: a DFT study of reactivity and site selectivity Journal of Physical Chemistry A, 111 (36). pp. 8823-8828. ISSN 1089-5639

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Official URL: http://pubs.acs.org/doi/abs/10.1021/jp072812o

Related URL: http://dx.doi.org/10.1021/jp072812o

Abstract

A site-selectivity model, based on the Fukui function as a local reactivity descriptor, has been applied to 1,2-disubstituted pyridinium ions incorporating two competing sites of similar reactivity, i.e., 1-methylene and 2-methylene, which may undergo deprotonation depending on the nature of substituent present on these moieties. Applicability of the local HSAB rule, in context with the Li-Evans' generalized HSAB principle suggesting the hard-hard interactions to be controlled by minimum Fukui function, has been illustrated. Global and local reactivity descriptors have been computed by carrying out DFT calculations at B3LYP/6-31++G∗∗ level using Mulliken and NPA methods for charge analysis. A comparison with the calculated deprotonation energies involving two sites indicates that the observed site selectivity in differently substituted pyridinium ions is better explained by the Li-Evans rule of minimum Fukui function for hard-hard interactions.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:25958
Deposited On:04 Dec 2010 10:50
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