Gas-phase structure of 2,2,2-trichloroethyl chloroformate studied by electron diffraction and quantum-chemical calculations

The molecular structure and conformational properties of 2,2,2-trichloroethyl chloroformate, ClC(O)OCH2CCl3 were determined experimentally using gas-phase electron diffraction (GED) and theoretically based on quantum-chemical calculations at the MP2 and DFT levels of theory. Further experimental mea...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2016-01, Vol.18 (1), p.393-402
Main Authors: Gil, Diego M, Tuttolomondo, María E, Blomeyer, Sebastian, Reuter, Christian G, Mitzel, Norbert W, Altabef, Aída Ben
Format: Article
Language:English
Subjects:
Chloroformate
Electron diffraction
Infrared spectroscopy
Mathematical analysis
Molecular structure
Quantum chemistry
Raman spectra
Symmetry
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Summary:The molecular structure and conformational properties of 2,2,2-trichloroethyl chloroformate, ClC(O)OCH2CCl3 were determined experimentally using gas-phase electron diffraction (GED) and theoretically based on quantum-chemical calculations at the MP2 and DFT levels of theory. Further experimental measurements such as UV-visible, IR and Raman spectroscopy were complemented with the corresponding theoretical studies. All experimental results and calculations confirm the presence of two conformers namely anti-gauche (C1 symmetry) and anti-anti (Cs symmetry). The conformational preference was rationalised by NBO and AIM analyses. Molecular properties such as ionisation potential, electronegativity, chemical potential, chemical hardness and softness were deduced from HOMO-LUMO analyses. The TD-DFT approach was applied to assign the electronic transitions observed in the UV-visible spectrum. A detailed interpretation of the infrared and Raman spectra of the title compound are reported. Using calculated frequencies as a guide, IR and Raman spectra also provide evidence for the presence of both C1 and Cs conformers.
ISSN:1463-9076
1463-9084
DOI:10.1039/c5cp05295e