2007/01/01 by Peter Politzer, Jane S. Murray, Pat Lane · 328 citations
Chemistry · Materials Science · #Catalysis #Chemical physics #Chemistry #Computational chemistry #Covalent bond #Crystallography #Crystallography and molecular interactions #Halogen bond #Hydrogen bond #Lewis acids and bases #Lone pair #Molecular Spectroscopy and Structure #Molecule #Non-covalent interactions #Nucleophile #Organic chemistry #Solid-state spectroscopy and crystallography
paper · doi:10.1002/qua.21419
published in International Journal of Quantum Chemistry 107(15), 3046-3052 (Wiley)
openalex publication_date 2007/01/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/29
Abstract In certain molecular environments, a covalently‐bonded atom from Groups V–VII may have a region of significantly‐positive electrostatic potential on its outer side, along the extension of a covalent bond. This is due to the electron‐deficient outer lobe of a half‐filled p bonding orbital, which is called a “σ‐hole.” σ‐Hole bonding is the resulting highly directional noncovalent interaction that may occur with a nucleophile, e.g., a lone pair of a Lewis base. In this article, we compare the computed interaction energies and vibrational frequency shifts associated with the formation of a series of σ‐hole‐bonded and hydrogen‐bonded complexes. When the molecular environments of the atoms of Groups V–VII and the hydrogen are similar, then the hydrogen bond is usually the stronger one, although there are exceptions, as in the case of bromine. Overall, however, σ‐hole bonding can certainly be competitive with hydrogen bonding. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007