Intramolecular Hydrogen Bond Energy in Polyhydroxy Systems: A Critical Comparison of Molecular Tailoring and Isodesmic Approaches

Deshmukh, Milind M. ; Suresh, Cherumuttathu H. ; Gadre, Shridhar R. (2007) Intramolecular Hydrogen Bond Energy in Polyhydroxy Systems: A Critical Comparison of Molecular Tailoring and Isodesmic Approaches The Journal of Physical Chemistry A, 111 (28). pp. 6472-6480. ISSN 1089-5639

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Official URL: http://doi.org/10.1021/jp071337r

Related URL: http://dx.doi.org/10.1021/jp071337r

Abstract

The intramolecular hydrogen bond (H-bond) energies in several polyhydroxy systems are estimated using an isodesmic/homodesmic reaction approach as well as a molecular tailoring approach (MTA) [Deshmukh, M. M.; Gadre, S. R.; Bartolotti, L. J. J. Phys. Chem. A2006, 110, 12519]. It is shown that the isodesmic/homodesmic reaction approach as advocated in the literature does not give true H-bond energy but includes the effect of strain energy due to the formation of a ring structure. Such a ring strain is duly accounted for in the MTA method. The isodesmic H-bond energies are found to be smaller than their MTA energy counterparts typically by the strain energy. The MTA is applied to decitol, a system with more than five different H-bonds for which an application of an appropriate isodesmic reaction is extremely difficult. It has been shown that the MTA method is able to predict not only the H-bond energies but also the trends in conformational energies for three different conformers of decitol studied in the present work.

Item Type:Article
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ID Code:127550
Deposited On:13 Oct 2022 10:53
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