σ-Holes, π-Holes and Electrostatically-Driven Interactions

Murray JS, Lane P, Clark T, Riley KE, Politzer P (2012)

Publication Type: Journal article

Publication year: 2012

Journal

Journal of Molecular Modeling Springer Verlag (Germany)

Book Volume: 18

Pages Range: 541-548

Journal Issue: 2

DOI: 10.1007/s00894-011-1089-1

Abstract

A positive \textgreekp-hole is a region of positive electrostatic potential that is perpendicular to a portion of a molecular framework. It is the counterpart of a \textgreeks-hole, which is along the extension of a covalent bond to an atom. Both \textgreeks-holes and \textgreekp-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 electronwithdrawing. Positive \textgreeks- and \textgreekp-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 \textgreekp-holecontaining 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 \textgreekp-hole bonding, a gradation is found from weakly noncovalent to considerably stronger with possible indications of some degree of coordinate covalency.

Authors with CRIS profile

Timothy Clark Computer-Chemie-Centrum (CCC)

Additional Organisation(s)

Exzellenz-Cluster Engineering of Advanced Materials (EAM)

Involved external institutions

CleveTheoComp LLC US United States (USA) (US) University of Puerto Rico (UPR) PR Puerto Rico (PR) University of New Orleans US United States (USA) (US)

How to cite

APA:

Murray, J.S., Lane, P., Clark, T., Riley, K.E., & Politzer, P. (2012). σ-Holes, π-Holes and Electrostatically-Driven Interactions. Journal of Molecular Modeling, 18(2), 541-548. https://doi.org/10.1007/s00894-011-1089-1

MLA:

Murray, Jane S., et al. "σ-Holes, π-Holes and Electrostatically-Driven Interactions." Journal of Molecular Modeling 18.2 (2012): 541-548.

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