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Halogen Bond: A Long Overlooked Interaction

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Book cover Halogen Bonding I

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 358))

Abstract

Because of their high electronegativity, halogen atoms are typically considered, in most of their derivatives, as sites of high electron density and it is commonly accepted that they can form attractive interactions by functioning as the electron donor site (nucleophilic site). This is the case when they work as hydrogen bond acceptor sites. However, the electron density in covalently bound halogens is anisotropically distributed. There is a region of higher electron density, accounting for the ability of halogens to function as electron donor sites in attractive interactions, and a region of lower electron density where the electrostatic potential is frequently positive (mainly in the heavier halogens). This latter region is responsible for the ability of halogen atoms to function as the electron-acceptor site (electrophilic site) in attractive interactions formed with a variety of lone pair-possessing atoms, anions, and π-systems. This ability is quite general and is shown by a wide diversity of halogenated compounds (e.g., organohalogen derivatives and dihalogens). According to the definition proposed by the International Union of Pure and Applied Chemistry, any attractive interactions wherein the halogen atom is the electrophile is named halogen bond (XB). In this chapter, it is discussed how the practice and the concept of XB developed and a brief history of the interaction is presented. Papers (either from the primary or secondary literature) which have reported major experimental findings in the field or which have given important theoretical contributions for the development of the concept are recollected in order to trace how a unifying and comprehensive categorization emerged encompassing all interactions wherein halogen atoms function as the electrophilic site.

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Notes

  1. 1.

    In Hassel’s structures the halogen molecules adopt a symmetrical location along the sixfold axis of benzene and form infinite ∙∙∙C6H6∙∙∙Br–Br∙∙∙C6H6∙∙∙Br–Br∙∙∙C6H6∙∙∙ chains. More recent X-ray measurements of the Br2∙∙∙C6H6 system at lower temperature than Hassel’s [55] reveal a less symmetric arrangement where bromine atoms are positioned over the rim of the benzene ring and the calculated hapticity (η = 1.52) is midway between the “over-atom” (η = 1.0) and “over-bond” (η = 2.0) coordination. A phase transition at 203 K leads to the diffraction pattern reported by Hassel and Strømme.

  2. 2.

    Lectures were given by: Peter Politzer (Cleveland State University, USA), Anthony C. Legon (University of Bristol, UK), Lee Brammer (University of Sheffield, UK), William Jones (University of Cambridge, UK), William T. Pennington (Clemson University, USA), Nancy S. Goroff (State University of New York, Stony Brook, USA), Milko E. van der Boom (The Weizmann Institute of Science, IL), Pierangelo Metrangolo (Politecnico di Milano, IT), Kari Rissanen (University of Jyväskylä, FL), Bernd Schöllhorn (Ecole Normale Supérieure Paris, FR), Duncan W. Bruce (University of York, UK), Hiroshi Yamamoto (RIKEN, JP), Shing P. Ho (Colorado State University, USA), and Patrick Lam (Bristol-Myers Squibb Research and Development, USA). Presented topics spanned modeling, crystal engineering, drug-receptor optimization, and material sciences.

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Acknowledgments

We are grateful to all colleagues, graduate and Ph.D. students, and postdoctoral associates who worked with us on XB. Some of them are mentioned in the references. Their dedication and enthusiasm has been fundamental. The authors are also grateful to the IUPAC for supporting the project no. 2009-032-1-100 “Categorizing Halogen Bonding and Other Noncovalent Interactions Involving Halogen Atoms.”

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  1. Laboratory of Nanostructured Fluorinated Materials (NFMLab), Department of Chemistry, Materials, and Chemical Engineering “Giulio Natta”, Politecnico di Milano, Via L. Mancinelli 7, 20131, Milano, Italy

    Gabriella Cavallo, Pierangelo Metrangolo, Tullio Pilati, Giuseppe Resnati & Giancarlo Terraneo

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  1. Gabriella Cavallo
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  1. Dipartimento di Chimica, Polytechnic University of Milan, Milano, Italy

    Pierangelo Metrangolo

  2. Dipartimento di Chimica, Polytechnic University of Milan, Milano, Italy

    Giuseppe Resnati

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Cavallo, G., Metrangolo, P., Pilati, T., Resnati, G., Terraneo, G. (2014). Halogen Bond: A Long Overlooked Interaction. In: Metrangolo, P., Resnati, G. (eds) Halogen Bonding I. Topics in Current Chemistry, vol 358. Springer, Cham. https://doi.org/10.1007/128_2014_573

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