title: Expansion of the sigma-hole concept.
abstract: The term "sigma-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 (sigma-hole bonding). The interaction is highly directional, along the extension of the covalent bond giving rise to the sigma-hole. Sigma-hole bonding has been observed, experimentally and computationally, for many covalently-bonded atoms of Groups V-VII. The positive character of the sigma-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 sigma-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 sigma-holes: (1) While the bonding orbital does require considerable p character, in view of the well-established highly directional nature of sigma-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.
authors.affiliation: Department of Chemistry, University of New Orleans, New Orleans, LA 70148, USA. jsmurray@uno.edu
authors.forename: Jane S
authors.initials: JS
authors.lastname: Murray
authors.forename: Pat
authors.initials: P
authors.lastname: Lane
authors.forename: Peter
authors.initials: P
authors.lastname: Politzer
mesh_terms: D001665:Binding Sites; D002251:Carbon Tetrachloride / Q000737:chemistry; D055598:Chemical Phenomena; D002713:Chlorine / Q000737:chemistry; D003198:Computer Simulation; D004583:Electrons; D006219:Halogens / Q000737:chemistry; D007700:Kinetics; D008737:Methyl Chloride / Q000737:chemistry; D008958:Models, Molecular; D010087:Oxides / Q000737:chemistry; D010758:Phosphorus / Q000737:chemistry; D012825:Silicon / Q000737:chemistry; D055672:Static Electricity; D013457:Sulfur Compounds / Q000737:chemistry; D013499:Surface Properties
chemical_list: D006219:Halogens; D010087:Oxides; D013457:Sulfur Compounds; D010758:Phosphorus; D002713:Chlorine; D008737:Methyl Chloride; D002251:Carbon Tetrachloride; D012825:Silicon