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σ-Holes, π-holes and electrostatically-driven interactions

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Abstract

A positive π-hole is a region of positive electrostatic potential that is perpendicular to a portion of a molecular framework. It is the counterpart of a σ-hole, which is along the extension of a covalent bond to an atom. Both σ-holes and π-holes become more positive (a) in going from the lighter to the heavier atoms in a given Group of the periodic table, and (b) as the remainder of the molecule is more electron-withdrawing. Positive σ- and π-holes can interact in a highly directional manner with negative sites, e.g., the lone pairs of Lewis bases. In this work, the complexes of 13 π-hole-containing molecules with the nitrogen lone pairs of HCN and NH3 have been characterized computationally using the MP2, M06-2X and B3PW91 procedures. While the electrostatic interaction is a major driving force in π-hole bonding, a gradation is found from weakly noncovalent to considerably stronger with possible indications of some degree of coordinate covalency.

Computed molecular surface electrostatic potential of SeO2 showing the π-hole above the selenium atom (middle). The position of the most positive electrostatic potential associated with the π-hole is indicated by a black hemisphere. Color ranges, in kcal mol-1, are: red, greater than 33; yellow, from 33 to 20; green, from 20 to 0; blue, less than 0 (negative).

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Acknowledgments

TC gratefully acknowledges the generous support of the Deutsche Forschungsgemeinschaft as part of SFB583 (Sonderforschungsbereich 583) “Redox-Active Metal Complexes: Control of Reactivity in Molecular Architecture” and KER the NSF (National Science Foundation) EPSCOR (Experimental Program to Stimulate Competitive Research) Program (Grant number EPS-0701525) and the NSF PREM (Partnership for Research & Education in Materials) Program (Grant number DMR-0934115).

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Authors and Affiliations

  1. CleveTheoComp, 1951 W, 59th Street Suite 409, Cleveland, OH, 44113, USA

    Jane S. Murray & Peter Politzer

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

    Pat Lane

  3. Computer-Chemie-Centrum and Interdisciplinary Center for Molecular Materials, Friedrich-Alexander-Universität, Erlangen-Nürnberg, Nägelsbachstraße 25, 91052, Erlangen, Germany

    Timothy Clark

  4. Centre for Molecular Design, University of Portsmouth, Mercantile House, Portsmouth, PO1 2EG, UK

    Timothy Clark

  5. Department of Chemistry, University of Puerto Rico, P.O. Box 23346, Rio Piedras, PR, 00931, USA

    Kevin E. Riley

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  1. Jane S. Murray
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  2. Pat Lane
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Correspondence to Jane S. Murray.

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Murray, J.S., Lane, P., Clark, T. et al. σ-Holes, π-holes and electrostatically-driven interactions. J Mol Model 18, 541–548 (2012). https://doi.org/10.1007/s00894-011-1089-1

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  • DOI: https://doi.org/10.1007/s00894-011-1089-1

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