Barrier to internal rotation, symmetry and carbonyl reactivity in methyl 3,3,3-trifluoropyruvate

Kevin Gregor Lengsfeld; Philipp Buschmann; Pavel Kats; Dirk Siekmann; Sven Herbers; Daniel Adam Obenchain; Stefanie Genuit; Cara Marie Höhne; Jens-Uwe Grabow

doi:10.1515/zpch-2020-0008

Published by De Gruyter (O) June 30, 2020

Barrier to internal rotation, symmetry and carbonyl reactivity in methyl 3,3,3-trifluoropyruvate

Kevin Gregor Lengsfeld , Philipp Buschmann , Pavel Kats , Dirk Siekmann , Sven Herbers , Daniel Adam Obenchain , Stefanie Genuit , Cara Marie Höhne and Jens-Uwe Grabow

From the journal Zeitschrift für Physikalische Chemie

https://doi.org/10.1515/zpch-2020-0008

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Abstract

High-resolution rotational spectroscopy was used to investigate the conformational landscape of methyl-3,3,3-trifluoropyruvate, a small, partially-fluorinated molecule, which is of interest because of its chemical properties and reactivity in contrast to the unfluorinated species. Methyl 3,3,3-trifluoropyruvate is also subject to two possible large amplitude motions of the methyl and trifluoromethyl group. However, only the methyl rotor gives rise to the tunneling splitting specific to individual conformers. In the rotational spectrum measured in the frequency region from 6 to 27 GHz, the identified conformers, s-cis and s-trans, were fitted to experimental accuracy, resulting in the accurate determination of the vibrational ground state rotational constants A0=2185.0582736 MHz, B0=1023.300 3117 MHz, and C0=803.52028795 MHz for the s-cis conformer, and A0=2706.9024(49) MHz, B0=864.889 539(81) MHz, and C0=746.532 896(71) MHz for the s-trans conformer. Additionally the barrier heights of the methyl rotor V3CH3=363.11694 cm−1 and V3(CH3)=389.290(80) cm−1 were obtained for the s-cis and s-trans conformer, respectively.

Keywords: inertial defect; internal rotation; large amplitude motion; methyl 3,3,3-trifluoropyruvate; microwave spectroscopy

Dedicated to:

Friedrich Temps on the occasion of his 65th birthday.

Corresponding author: Kevin Gregor Lengsfeld, Institut für Physikalische Chemie und Elektrochemie Leibniz Universität Hannover, Callinstraße, 3a, 30167Hannover, Germany E-mail: kevin.lengsfeld@pci.uni-hannover.de

Funding source: Verband der Chemischen Industrie

Funding source: Deutsche Forschungsgemeinschaft

Funding source: Alexander von Humboldt Foundation

Funding source: Fonds der Chemischen Industrie

Acknowledgments

We wish to thank the Land Niedersachsen, the Deutsche Forschungsgemeinschaft, DAO wishes to thank the Alexander von Humboldt Foundation and KGL wishes to thank the Fonds der Chemischen Industrie for fellowship.

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Supplementary Material

The online version of this article offers supplementary material (https://doi.org/10.1515/zpch-2020-0008).

Received: 2019-12-27

Accepted: 2020-03-24

Published Online: 2020-06-30

Published in Print: 2020-08-27

Barrier to internal rotation, symmetry and carbonyl reactivity in methyl 3,3,3-trifluoropyruvate

Abstract

Dedicated to:

Acknowledgments

References

Supplementary Material

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