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Issue 28, 2010
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Halogen bonding: an electrostatically-driven highly directional noncovalent interaction

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Abstract

A halogen bond is a highly directional, electrostatically-driven noncovalent interaction between a region of positive electrostatic potential on the outer side of the halogen X in a molecule R–X and a negative site B, such as a lone pair of a Lewis base or the π-electrons of an unsaturated system. The positive region on X corresponds to the electronically-depleted outer lobe of the half-filled p-type orbital of X that is involved in forming the covalent bond to R. This depletion is labeled a σ-hole. The resulting positive electrostatic potential is along the extension of the R–X bond, which accounts for the directionality of halogen bonding. Positive σ-holes can also be found on covalently-bonded Group IV–VI atoms, which can similarly interact electrostatically with negative sites. Since positive σ-holes often exist in conjunction with negative potentials on other portions of the atom's surface, such atoms can interact electrostatically with both nucleophiles and electrophiles, as has been observed in surveys of crystallographic structures. Experimental as well as computational studies indicate that halogen and other σ-hole interactions can be competitive with hydrogen bonding, which itself can be viewed as a subset of σ-hole bonding.

Graphical abstract: Halogen bonding: an electrostatically-driven highly directional noncovalent interaction

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Publication details

The article was received on 11 Mar 2010, accepted on 21 May 2010 and first published on 22 Jun 2010


Article type: Perspective
DOI: 10.1039/C004189K
Citation: Phys. Chem. Chem. Phys., 2010,12, 7748-7757
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    Halogen bonding: an electrostatically-driven highly directional noncovalent interaction

    P. Politzer, J. S. Murray and T. Clark, Phys. Chem. Chem. Phys., 2010, 12, 7748
    DOI: 10.1039/C004189K

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