Communication: A hydrogen-bonded difluorocarbene complex: Ab initio and matrix isolation study

• Published in: The Journal of chemical physics 2017-10, Vol.147 (13), p.131102-131102
• Main Authors: Sosulin, Ilya S., Shiryaeva, Ekaterina S., Tyurin, Daniil A., Feldman, Vladimir I.
• Format: Article
• Language: English
• Subjects: Bonding strength; Chemical reactions; Fourier transforms; Hydrogen bonding; Infrared spectroscopy; Libration; Mathematical analysis; Organic chemistry; Spectrum analysis; Stretching; Trifluoromethane; X ray irradiation; Xenon
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.4999772

Structure and spectroscopic features of the CF2⋯HF complexes were studied by ab initio calculations at the CCSD(T) level and matrix isolation FTIR spectroscopy. The calculations predict three stable structures. The most energetically favorable structure corresponds to hydrogen bonding of HF to the lone pair of the C atom (the interaction energy of 3.58 kcal/mol), whereas two less stable structures are the H⋯F bonded complexes (the interaction energies of 0.30 and 0.24 kcal/mol). The former species was unambiguously characterized by the absorptions in the FTIR spectra observed after X-ray irradiation of fluoroform in a xenon matrix at 5 K. The corresponding features appear at 3471 (H–F stretching), 1270 (C–F symmetric stretching, shoulder), 1175 (antisymmetric C–F stretching), and 630 (libration) cm−1, in agreement with the computational predictions. To our knowledge, it is the first hydrogen-bonded complex of dihalocarbene. Possible weaker manifestations of the H⋯F bonded complexes were also found in the C–F stretching region; however, their assignment is tentative. The H⋯C bonded complex is protected from reaction yielding a fluoroform molecule by a remarkably high energy barrier (23.85 kcal/mol), so it may be involved in various chemical reactions.