Halogen bonding and other sigma-hole interactions: a perspective
Politzer P, Murray JS, Clark T (2013)
Publication Status: Published
Publication Type: Journal article
Publication year: 2013
Journal
Publisher: Royal Society of Chemistry
Book Volume: 15
Pages Range: 11178-11189
Journal Issue: 27
DOI: 10.1039/c3cp00054k
Abstract
A sigma-hole bond is a noncovalent interaction between a covalently-bonded atom of Groups IV-VII and a negative site, e.g. a lone pair of a Lewis base or an anion. It involves a region of positive electrostatic potential, labeled a sigma-hole, on the extension of one of the covalent bonds to the atom. The sigma-hole is due to the anisotropy of the atom's charge distribution. Halogen bonding is a subset of sigma-hole interactions. Their features and properties can be fully explained in terms of electrostatics and polarization plus dispersion. The strengths of the interactions generally correlate well with the magnitudes of the positive and negative electrostatic potentials of the sigma-hole and the negative site. In certain instances, however, polarizabilities must be taken into account explicitly, as the polarization of the negative site reaches a level that can be viewed as a degree of dative sharing (coordinate covalence). In the gas phase, sigma-hole interactions with neutral bases are often thermodynamically unfavorable due to the relatively large entropy loss upon complex formation.
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APA:
Politzer, P., Murray, J.S., & Clark, T. (2013). Halogen bonding and other sigma-hole interactions: a perspective. Physical Chemistry Chemical Physics, 15(27), 11178-11189. https://dx.doi.org/10.1039/c3cp00054k
MLA:
Politzer, Peter, Jane S. Murray, and Timothy Clark. "Halogen bonding and other sigma-hole interactions: a perspective." Physical Chemistry Chemical Physics 15.27 (2013): 11178-11189.
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