Cooperative effects of hydrogen, halogen and beryllium bonds on model halogen-bonded FCl … YZ (YZ = BF, CO, N 2 ) complexes in FX′ … FCl … YZ trimers (FX′ = FH, FCl, F 2 Be)Molecular Physics

About

Authors
Sean A.C. McDowell, Dania S. Hamilton
Year
2015
DOI
10.1080/00268976.2015.1027755
Subject
Physical and Theoretical Chemistry / Biophysics / Molecular Biology / Condensed Matter Physics

Similar

Interplay between halogen bonds and hydrogen bonds in OH/SH···HOX···HY (X = Cl, Br; Y = F, Cl, Br) complexes

Authors:
Wenjie Wu, Yanli Zeng, Xiaoyan Li, Xueying Zhang, Shijun Zheng, Lingpeng Meng
2012

Structural Competition between Hydrogen Bonds and Halogen Bonds

Authors:
Christer B. Aakeröy, Meg Fasulo, Nate Schultheiss, John Desper, Curtis Moore
2007

Hepatic artery infusion chemotherapy: gastroduodenal complications

Authors:
VP Chuang, S Wallace, J Stroehlein, HY Yap, YZ Patt
1981

S N 2-like Reaction in Hydrogen-Bonded Complexes:  A Theoretical Study

Authors:
Weizhou Wang, Yu Zhang, Kaixun Huang
2005

Text

This article was downloaded by: [University of Montana]

On: 08 April 2015, At: 12:02

Publisher: Taylor & Francis

Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK

Click for updates

Molecular Physics: An International Journal at the

Interface Between Chemistry and Physics

Publication details, including instructions for authors and subscription information: http://www.tandfonline.com/loi/tmph20

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

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the

Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and should be independently verified with primary sources of information. Taylor and Francis shall not be liable for any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of the Content.

This article may be used for research, teaching, and private study purposes. Any substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http:// www.tandfonline.com/page/terms-and-conditions

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

Introduction

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: sacm@mail.com †

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.