, Volume 18, Issue 2, pp 541-548
Date: 04 May 2011

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

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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).