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Issue 27, 2013
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Halogen bonding and other σ-hole interactions: a perspective

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Abstract

A σ-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 σ-hole, on the extension of one of the covalent bonds to the atom. The σ-hole is due to the anisotropy of the atom's charge distribution. Halogen bonding is a subset of σ-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 σ-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, σ-hole interactions with neutral bases are often thermodynamically unfavorable due to the relatively large entropy loss upon complex formation.

Graphical abstract: Halogen bonding and other σ-hole interactions: a perspective

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Publication details

The article was received on 07 Jan 2013, accepted on 19 Feb 2013 and first published on 19 Feb 2013


Article type: Perspective
DOI: 10.1039/C3CP00054K
Citation: Phys. Chem. Chem. Phys., 2013,15, 11178-11189
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    Halogen bonding and other σ-hole interactions: a perspective

    P. Politzer, J. S. Murray and T. Clark, Phys. Chem. Chem. Phys., 2013, 15, 11178
    DOI: 10.1039/C3CP00054K

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