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Cooperative effects of hydrogen, halogen and beryllium bonds on model halogen-bonded FCl … YZ (YZ = BF, CO, N2) complexes in FX′ … FCl … YZ trimers (FX′ =
FH, FCl, F2Be)
Sean A.C. McDowella & Dania S. Hamiltona a Department of Biological and Chemical Sciences, The University of the West Indies, Cave
Hill Campus, Barbados
Published online: 01 Apr 2015.
To cite this article: Sean A.C. McDowell & Dania S. Hamilton (2015): Cooperative effects of hydrogen, halogen and beryllium bonds on model halogen-bonded FCl … YZ (YZ = BF, CO, N2) complexes in FX′ … FCl … YZ trimers (FX′ = FH, FCl, F2Be), Molecular
Physics: An International Journal at the Interface Between Chemistry and Physics, DOI: 10.1080/00268976.2015.1027755
To link to this article: http://dx.doi.org/10.1080/00268976.2015.1027755
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Molecular Physics, 2015 http://dx.doi.org/10.1080/00268976.2015.1027755
SPECIAL ISSUE IN HONOUR OF NICHOLAS C. HANDY
Cooperative effects of hydrogen, halogen and beryllium bonds on model halogen-bonded
FCl . . .YZ (YZ = BF, CO, N2) complexes in FX′ . . .FCl . . .YZ trimers (FX′ = FH, FCl, F2Be)
Sean A.C. McDowell∗,† and Dania S. Hamilton†
Department of Biological and Chemical Sciences, The University of the West Indies, Cave Hill Campus, Barbados (Received 18 February 2015; accepted 5 March 2015)
A computational study of model halogen-bonded FCl . . .YZ dimers and FX′ . . .FCl . . .YZ (FX′ = FH, FCl, F2Be; YZ =
BF, CO, N2) trimers was undertaken at the MP2/6-311+ +G (2d, 2p) level of theory. Three different trimer arrangements are possible and the cooperative effect of hydrogen-, halogen- and beryllium-bonding in each of these trimers was assessed relative to the FCl . . .YZ dimer. It was found that the beryllium bond has the largest cooperative effect, while the halogen bond has the smallest, with the hydrogen bond being intermediate between the other two interactions. Interesting trends in selected properties were identified and discussed.
Keywords: cooperativity; halogen bond; beryllium bond; hydrogen bond
Non-covalent interactions continue to be a topic of considerable interest to chemists. The possibility of modifying and controlling the structure and reactivity of clusters of molecules, through an understanding of the important forces between these molecules, is a strong motivation for studying such types of interactions.
The hydrogen bond is by far the most widely studied of all intermolecular interactions, especially due to its importance in controlling biological activity and its central role in many natural processes [1–6]. However, the halogen bond has attracted substantial interest over the last 10 years or so due to its great potential for technological applications arising from its directionality and the possibility of modifying its strength in a controlled fashion [7–11]. It bears some similarity to the hydrogen bond in a number of respects and its potential for applications spans several important fields, including crystal engineering and drug design [12–15].
For hydrogen-bonded complexes, A–H . . .Y, where A is an electron-withdrawing atom or group of atoms and Y is an atom or group of atoms containing nucleophilic sites (e.g. lone pairs), the unshielded proton interacts directly with the nucleophilic site on Y. By contrast, for halogenbonded complexes, A–X . . .Y (X= halogen atom), a region of maximum positive electrostatic potential along the extension of the A–X bond (the so-called ‘σ -hole’) interacts with the electron-rich site on Y. The anisotropic electron ∗
Corresponding author. Email: firstname.lastname@example.org †
The authors wish to dedicate this paper in memory of Professor Nicholas Handy FRS, a truly outstanding theoretical chemist. One of us (SACM) had the pleasure of a long and cordial association with Nicholas, being fortunate to have also briefly worked with Nicholas and
Dr Roger Amos and publishing in Chemical Physics Letters a seminal study of molecular polarisabilities, in which the more established ab initio techniques were compared with the then-emerging DFT methods. distribution on the halogen X surface allows for additional binding of an electrophile to the lone pairs on X in a direction roughly perpendicular to the A–X molecular axis.