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

Author:

Lengsfeld Kevin Gregor1,Buschmann Philipp1,Kats Pavel1,Siekmann Dirk1,Herbers Sven1,Adam Obenchain Daniel1,Genuit Stefanie1,Höhne Cara Marie1,Grabow Jens-Uwe1

Affiliation:

1. Institut für Physikalische Chemie und Elektrochemie Leibniz Universität Hannover , Callinstraße, 3a , 30167 Hannover , Germany

Abstract

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 A 0 = 2185.05827 36  MHz ${A}_{0}=2185.05827\left(36\right)\text{\hspace{0.17em}MHz}$ , B 0 = 1023.300   31 17  MHz ${B}_{0}=1023.30031\left(17\right)\text{\hspace{0.17em}MHz}$ , and C 0 = 803.520287 95  MHz ${C}_{0}=803.520287\left(95\right)\text{\hspace{0.17em}MHz}$ for the s-cis conformer, and A 0 = 2706.9024 ( 49 )  MHz ${A}_{0}=2706.9024\left(49\right)\text{\hspace{0.17em}MHz}$ , B 0 = 864.889   539 ( 81 )  MHz ${B}_{0}=864.889539\left(81\right)\text{\hspace{0.17em}MHz}$ , and C 0 = 746.532   896 ( 71 )  MHz ${C}_{0}=746.532896\left(71\right)\text{\hspace{0.17em}MHz}$ for the s-trans conformer. Additionally the barrier heights of the methyl rotor V 3 CH 3 = 363 . 116 94  cm 1 ${V}_{3}\left({\text{CH}}_{3}\right)=363.116\left(94\right){\text{\hspace{0.17em}cm}}^{-1}$ and V 3 ( CH 3 ) = 389.290 ( 80 )  cm 1 ${V}_{3}\left({\text{CH}}_{3}\right)=389.290\left(80\right){\text{\hspace{0.17em}cm}}^{-1}$ were obtained for the s-cis and s-trans conformer, respectively.

Funder

Verband der Chemischen Industrie

Deutsche Forschungsgemeinschaft

Alexander von Humboldt Foundation

Fonds der Chemischen Industrie

Publisher

Walter de Gruyter GmbH

Subject

Physical and Theoretical Chemistry

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