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

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)kJmol−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)kJmol−1. Furthermore, indications of the presence of a small amount of the halogen bonded complex are also observed.