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CH hydrogen bonding: 3. Hammett correlations for phenylacetonitriles and tetrafluorobenzenes with HMPA
Author(s) -
Lorand John P.
Publication year - 2011
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1740
Subject(s) - chemistry , covalent bond , hydrogen bond , intermolecular force , chemical polarity , computational chemistry , chemical bond , crystallography , molecule , organic chemistry
Understanding the hydrogen bond, or H‐bond, arguably the strongest known intermolecular attractive force, is of great importance. Models of H‐bonding hold that both electrostatic and covalent components are at work. H‐bonding of CH bonds, and thus presumably other AH bonds, is greatly facilitated by polar substituents. We have found that equilibrium constants, K, for CH H‐bonding in series of phenylacetonitriles and tetrafluorobenzenes with HMPA are closely correlated by the Hammett equation. That is, K values vary as substituents of different polarities are introduced at positions remote from the donor CH bond. This result is consistent with a significant electrostatic component in these examples of H‐bonding. It may, however, also be explained by interaction with the σ * orbital of the CH bond, which is involved in the covalent component of the H‐bond. Theoretical models need to be applied to this and other cases. Copyright © 2010 John Wiley & Sons, Ltd.