Competition of C(sp2)–X···O Halogen Bonding and Lone Pair···π Interactions: Cryospectroscopic Study of the Complexes of C2F3X (X = F, Cl, Br, and I) and Dimethyl Ether

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 119; no. 11; pp. 2502 - 2516
• Main Authors: Geboes, Yannick, Nagels, Nick, Pinter, Balazs, De Proft, Frank, Herrebout, Wouter A
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 19.03.2015
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp5087812

Inspection of the electrostatic potential of C2F3X (X = F, Cl, Br, and I) revealed a second electropositive region in the immediate vicinity of the CC double bond apart from the σ hole of chlorine, bromine, and iodine, leading to C(sp2)–X···Y halogen bonding, through which complexes stabilized by so-called lone pair···π interactions can be formed. Consequently, the experimental studies for the complexes of dimethyl ether with C2F3X (X = F, Cl, Br, and I) not only allowed one to experimentally characterize and rationalize the effects of hybridization on halogen bonding but, for the first time, also allowed the competition of C–X···Y halogen bonding and lone pair···π interactions to be studied at thermodynamic equilibrium. Analysis of the infrared and Raman spectra reveals that in the cryosolutions of dimethyl ether and C2F3I, solely the halogen-bonded complex is present, whereas C2F3Br and C2F3Cl give rise to a lone pair···π bonded complex as well as a halogen-bonded complex. Mixtures of dimethyl ether with C2F4 solely yield a lone pair···π bonded complex. The experimentally derived complexation enthalpies for the halogen bonded complexes are found to be −14.2(5) kJ mol–1 for C2F3I·DME and −9.3(5) kJ mol–1 for C2F3Br·DME. For the complexes of C2F3Cl with dimethyl ether, no experimental complexation enthalpy could be obtained, whereas the C2F4·DME complex has a complexation enthalpy of −5.5(3) kJ mol–1. The observed trends have been rationalized with the aid of an interaction energy decomposition analysis (EDA) coupled to a Natural Orbital for Chemical Valence (NOCV) analysis and also using the noncovalent interaction index method.