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σ-hole bonding: molecules containing group VI atoms

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Abstract

It has been observed both experimentally and computationally that some divalently-bonded Group VI atoms interact in a noncovalent but highly directional manner with nucleophiles. We show that this can readily be explained in terms of regions of positive electrostatic potential on the outer surfaces of such atoms, these regions being located along the extensions of their existing covalent bonds. These positive regions can interact attractively with the lone pairs of nucleophiles. The existence of such a positive region is attributed to the presence of a “σ-hole.” This term designates the electron-deficient outer lobe of a half-filled p bonding orbital on the Group VI atom. The positive regions become stronger as the electronegativity of the atom decreases and its polarizability increases, and as the groups to which it is covalently bonded become more electron-withdrawing. We demonstrate computationally that the σ-hole concept and the outer regions of positive electrostatic potential account for the existence, directionalities and strengths of the observed noncovalent interactions.

Calculated B3PW91/6-31G** electrostatic potential of F2S, computed on the 0.001 electrons/bohr3 contour of the electronic density. The sulfur atom is toward the reader; the red areas indicate the most positive potentials, reaching +34.4 kcal/mole, along the extensions of the F-S bonds. The purple region (negative) on the left and the one (not totally visible) on the right side of the sulfur are due to its nonbonded s and p electrons. The fluorines (top left and bottom left) also have negative regions of potential (purple areas)

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Authors and Affiliations

  1. Department of Chemistry, Cleveland State University, Cleveland, OH, 44115, USA

    Jane S. Murray & Peter Politzer

  2. Department of Chemistry, University of New Orleans, New Orleans, LA, 70148, USA

    Pat Lane & Peter Politzer

  3. Computer-Chemie-Centrum, Friedrich-Alexander-Universität Erlangen-Nürnberg, Nägelsbachstraße 25, 91052, Erlangen, Germany

    Timothy Clark

Authors
  1. Jane S. Murray
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  2. Pat Lane
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  3. Timothy Clark
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  4. Peter Politzer
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Correspondence to Jane S. Murray.

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Murray, J.S., Lane, P., Clark, T. et al. σ-hole bonding: molecules containing group VI atoms. J Mol Model 13, 1033–1038 (2007). https://doi.org/10.1007/s00894-007-0225-4

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  • DOI: https://doi.org/10.1007/s00894-007-0225-4

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