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Zeitschrift für Naturforschung B

A Journal of Chemical Sciences


IMPACT FACTOR 2017: 0.757

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1865-7117
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Volume 71, Issue 12

Issues

Structure and bonding of 2,2,2-trichloroethylacetate: An experimental gas phase and computational study

Sebastian Blomeyer
  • Chair of Inorganic and Structural Chemistry, Faculty of Chemistry and Center for Molecular Materials CM2, Bielefeld University, Universitätsstraße 25, D-33615 Bielefeld, Germany
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Christian G. Reuter
  • Chair of Inorganic and Structural Chemistry, Faculty of Chemistry and Center for Molecular Materials CM2, Bielefeld University, Universitätsstraße 25, D-33615 Bielefeld, Germany
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Diego M. Gil
  • INQUINOA (CONICET-UNT), Instituto de Química Física, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, San Lorenzo 456, T4000CAN, San Miguel de Tucumán, R. Argentina
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ María E. Tuttolomondo
  • INQUINOA (CONICET-UNT), Instituto de Química Física, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, San Lorenzo 456, T4000CAN, San Miguel de Tucumán, R. Argentina
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Aída Ben Altabef
  • INQUINOA (CONICET-UNT), Instituto de Química Física, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, San Lorenzo 456, T4000CAN, San Miguel de Tucumán, R. Argentina
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  • De Gruyter OnlineGoogle Scholar
/ Norbert W. Mitzel
  • Corresponding author
  • Chair of Inorganic and Structural Chemistry, Faculty of Chemistry and Center for Molecular Materials CM2, Bielefeld University, Universitätsstraße 25, D-33615 Bielefeld, Germany, Fax: Int +(0)521 106 6026
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Published Online: 2016-10-08 | DOI: https://doi.org/10.1515/znb-2016-0166

Abstract

The structural and conformational properties of 2,2,2-trichloroethylacetate, H3CCO2CH2CCl3, have been determined in the gas phase using gas electron diffraction (GED). The experimental measurements were complemented by MP2 and DFT quantum-chemical calculations. Two conformers separated by a shallow rotational barrier have been identified, one of C1 (syn-gauche) and the other of Cs symmetry (syn-anti). All calculations indicate that syn-gauche is preferred in terms of enthalpy, whereas syn-anti seems to be slightly more stable regarding Gibbs free energy. In the gas-phase structure determination, dynamic models based on different potential energy surface scans were used. The one from dispersion-corrected density functional theory, predicting a preference of syn-gauche by 1.7kJmol−1, was found to describe the experimental data best. One- and two-conformer models had to be rejected due to correlations and unrealistically large amplitudes. Experimentally determined structural parameters are in good agreement with both, quantum-chemical calculations as well as GED data for related compounds. Interacting quantum atoms (IQA) analyses revealed that interplay between the carbonyl group and the hydrogen as well as chlorine atoms of the trichloroethyl group accounts for most of the stabilisation of the C1 conformer. With intramolecular symmetry-adapted perturbation theory (I-SAPT) analyses it was possible to further elucidate the nature of dominant interactions in the two conformers. Herein, preference of syn-gauche can for the most part be attributed to electrostatic and to some extent to induction and dispersion interplays. In contrast this conformer is severely destabilised through steric repulsion. These results were supported by NBO analyses.

This article offers supplementary material which is provided at the end of the article.

Keywords: 2,2,2-Trichloroethylacetate; gas electron diffraction

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About the article

Received: 2016-07-22

Accepted: 2016-08-29

Published Online: 2016-10-08

Published in Print: 2016-12-01


Citation Information: Zeitschrift für Naturforschung B, Volume 71, Issue 12, Pages 1253–1260, ISSN (Online) 1865-7117, ISSN (Print) 0932-0776, DOI: https://doi.org/10.1515/znb-2016-0166.

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