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Expansion of the σ-hole concept

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Abstract

The term “σ-hole” originally referred to the electron-deficient outer lobe of a half-filled p (or nearly p) orbital involved in forming a covalent bond. If the electron deficiency is sufficient, there can result a region of positive electrostatic potential which can interact attractively (noncovalently) with negative sites on other molecules (σ-hole bonding). The interaction is highly directional, along the extension of the covalent bond giving rise to the σ-hole. σ-Hole bonding has been observed, experimentally and computationally, for many covalently-bonded atoms of Groups V–VII. The positive character of the σ-hole increases in going from the lighter to the heavier (more polarizable) atoms within a Group, and as the remainder of the molecule becomes more electron-withdrawing. In this paper, we show computationally that significantly positive σ-holes, and subsequent noncovalent interactions, can also occur for atoms of Group IV. This observation, together with analogous ones for the molecules (H3C)2SO, (H3C)2SO2 and Cl3PO, demonstrates a need to expand the interpretation of the origins of σ-holes: (1) While the bonding orbital does require considerable p character, in view of the well-established highly directional nature of σ-hole bonding, a sizeable s contribution is not precluded. (2) It is possible for the bonding orbital to be doubly-occupied and forming a coordinate covalent bond.

Two views of the calculated electrostatic potential on the 0.001 au molecular surface of SiCl4. Color ranges, in kcal/mole, are: purple, negative; blue, between 0 and 8; green, between 8 and 11; yellow, between 11 and 18; red, more positive than 18. The top view shows three of the four chlorines. In the center is the σ-hole due to the fourth Cl−Si bond, its most positive portion (red) being on the extension of that bond. In the bottom view are visible two of the σ-holes on the silicon. In both views can be seen the σ-holes on the chlorines, on the extensions of the Si−Cl bonds; their most positive portions are green

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Authors and Affiliations

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

    Jane S. Murray, Pat Lane & Peter Politzer

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

    Jane S. Murray & Peter Politzer

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

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Murray, J.S., Lane, P. & Politzer, P. Expansion of the σ-hole concept. J Mol Model 15, 723–729 (2009). https://doi.org/10.1007/s00894-008-0386-9

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  • DOI: https://doi.org/10.1007/s00894-008-0386-9

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