کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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5373041 | 1504192 | 2016 | 8 صفحه PDF | دانلود رایگان |
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 pairâ¯Ï 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 pairâ¯Ï bonded complex is found in solution, with an experimental complexation enthalpy of â14.5(3) kJ molâ1. For COFCl·DME three lone pairâ¯Ï complexes, as well as a Clâ¯O halogen bonded complex, are found from ab initio calculations. Experimentally, clear complex bands for 1:1 lone pairâ¯Ï complexes are observed, with an experimental complexation enthalpy of â11.4(2) kJ molâ1. Furthermore, indications of the presence of a small amount of the halogen bonded complex are also observed.
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Journal: Chemical Physics - Volume 476, 12 September 2016, Pages 1-8