Title
Lone <tex>$pair\cdots\pi$</tex> interactions involving carbonyl <tex>$\pi$</tex>-systems : experimental and theoretical study of the complexes of <tex>$COF_{2}$</tex> and COFCl with dimethyl ether
Author
Faculty/Department
Faculty of Sciences. Chemistry
Publication type
article
Publication
Amsterdam ,
Subject
Physics
Chemistry
Source (journal)
Chemical physics. - Amsterdam
Volume/pages
476(2016) , p. 1-8
ISSN
0301-0104
ISI
000384021900001
Carrier
E
Target language
English (eng)
Full text (Publishers DOI)
Affiliation
University of Antwerp
Abstract
In this theoretical and experimental study, the ability of carbonyl fluoride (COF2) and carbonyl chloride fluoride (COFCl) to form noncovalent interactions with the Lewis base dimethyl ether (DME) is assessed. From ab initio calculations, two stable complexes are found for COF2·DME, both formed through a lone pair···π interaction. FTIR measurements on liquefied noble gas solutions, supported by ab initio calculations, statistical thermodynamical calculations and Monte Carle Free Energy Perturbation calculations, show that a 1:1 lone pair···π bonded complex is found in solution, with an experimental complexation enthalpy of -14.5(3) kJ mol-1. For COFCl·DME three lone pair···π complexes, as well as a Cl···O halogen bonded complex, are found from ab initio calculations. Experimentally, clear complex bands for 1:1 lone pair···π complexes are observed, with an experimental complexation enthalpy of -11.4(2) kJ mol-1. Furthermore, indications of the presence of a small amount of the halogen bonded complex are also observed.
Full text (open access)
https://repository.uantwerpen.be/docman/irua/7a7cdd/134482.pdf
E-info
https://repository.uantwerpen.be/docman/iruaauth/0da2cc/134482.pdf
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