Lone pair⋯π interactions involving carbonyl π-systems: Experimental and theoretical study of the complexes of COF₂ and COFCl with dimethyl ether

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• 作者：Yannick Geboes^a ; ^b ; Frank De Proft^b ; Wouter A. Herrebout^a ; ^{wouter.herrebout@uantwerpen.be" class="auth_mail" title="E-mail the corresponding author}
• 关键词：lp⋯π interactions ; Halogen bonding ; FTIR ; Cryospectroscopy
• 刊名：Chemical Physics
• 出版年：2016
• 出版时间：12 September 2016
• 年：2016
• 卷：476
• 期：Complete
• 页码：1-8
• 全文大小：730 K

文摘

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.