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

Тип документаJournal Article
Дата публикации2017-10-07
Название журналаJournal of Chemical Physics
  • Physical and Theoretical Chemistry
  • General Physics and Astronomy
Краткое описание
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.
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1. Sosulin I.S. и др. Communication: A hydrogen-bonded difluorocarbene complex:Ab initioand matrix isolation study // The Journal of Chemical Physics. 2017. Т. 147. № 13. С. 131102.


DO - 10.1063/1.4999772

UR -

TI - Communication: A hydrogen-bonded difluorocarbene complex:Ab initioand matrix isolation study

T2 - The Journal of Chemical Physics

AU - Sosulin, Ilya S.

AU - Shiryaeva, Ekaterina S.

AU - Tyurin, Daniil A.

AU - Feldman, Vladimir I.

PY - 2017

DA - 2017/10/07

PB - AIP Publishing

SP - 131102

IS - 13

VL - 147

SN - 0021-9606

SN - 1089-7690

ER -

BibTex |


doi = {10.1063/1.4999772},

url = {},

year = 2017,

month = {oct},

publisher = {{AIP} Publishing},

volume = {147},

number = {13},

pages = {131102},

author = {Ilya S. Sosulin and Ekaterina S. Shiryaeva and Daniil A. Tyurin and Vladimir I. Feldman},

title = {Communication: A hydrogen-bonded difluorocarbene complex:Ab initioand matrix isolation study}


Sosulin, Ilya S. et al. “Communication: A Hydrogen-Bonded Difluorocarbene complex:Ab Initioand Matrix Isolation Study.” The Journal of Chemical Physics 147.13 (2017): 131102. Crossref. Web.