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\title{TUNING THE METHYL TORSION IN 2-METHYLTHIOPHENE DERIVATIVES BY RING SUBSTITUTION}

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\author{\underline{\FirstName K.~J. \LastName KOZIOL}$^1$,
  \FirstName H.~V.~L. \LastName NGUYEN$^{1,2}$}
\address{$^1$Univ Paris Est Cr\'{e}teil and Universit\'{e} Paris Cit\'{e}, CNRS, LISA, 94010 Cr\'{e}teil, France, $^2$Institut Universitaire de France (IUF), 1 Rue Descartes, 75231 Paris, France}

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\fancyhead[C]{{\footnotesize \textit{HRMS, 28th Colloquium, Dijon, France,
  Aug. 28 - Sept. 1, 2023}}}
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\category {4,12}
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\index{Microwave spectroscopy}
\index{Internal Rotation}
\index{Large Amplitude Motion}
\index{2-methylthiophene}
\index{2-chloro-5-methylthiophene}

%% Place the body of your abstract below.
2-methylthiophene (2MTP) features a methyl group at the 2-position of the thiophene ring that undergoes internal rotation hindered by a $V_3$ barrier of 197.6 cm$^{-1}$.\footnote{\href{https://dx.doi.org/10.3390/spectroscj1010005}{doi:10.3390/spectroscj1010005}, K.~J. Koziol, H.~El~Hadki, A.~L\"{u}chow, 
 N.~Vogt, J.~Demaison, H.~V.~L.~Nguyen, \textit{Spectrosc. J.} \textbf{1}, 49-64 (2023).} Adding another substituent at the 5-position has a major impact on the barrier height, which appeared to be of electronic origin due to the absence of sterical hindrance. If a chlorine atom is present at the 5-position, as in 2-chloro-5-methylthiophene (2Cl5MTP), the $V_3$ barrier increases to 246.2 cm$^{-1}$. Being separated by the sulfur atom, the apparent influence of chlorine on the methyl internal rotation can only be explained by electronic properties transferred through the $\pi$-conjugated system. While it is surprising that replacing the chlorine atom that has a strong $-$I and $+$M effect with a second methyl group, as in 2,5-dimethylthiophene, leads to a minor change in the $V_3$ barrier (248.0 cm$^{-1}$),\footnote{\href{https://dx.doi.org/10.1039/C5CP03513A}{doi:10.1039/C5CP03513A}, V. Van, W. Stahl, H. V. L. Nguyen, \textit{Phys. Chem. Chem. Phys.} \textbf{17} 32111-32114 (2015).} replacing it with an acetyl group as in \textit{syn}-2-acetyl-5-methylthiophene greatly reduced the barrier to 157.3 cm$^{-1}$.\footnote{\href{https://dx.doi.org/10.1039/D2CP03897H}{doi:10.1039/D2CP03897H}, C. Dindic, H. V. L. Nguyen, \textit{Phys. Chem. Chem. Phys.} \textbf{25}, 509-519 (2023).} Comparison of the barriers to those of the corresponding furan derivates shows a large impact of the hetero atom with an increase to 412.9 cm$^{-1}$ for 2-methylfuran,\footnote{\href{https://dx.doi.org/10.1016/j.jms.2012.06.005}{doi:10.1016/j.jms.2012.06.005}, I. A. Finneran, S. T. Shipman, S. L. W. Weaver, \textit{J. Mol. Spectrosc.} \textbf{280}, 27-33 (2012).} 439.1 cm$^{-1}$ for 2,5-dimethylfuran,\footnote{\href{https://dx.doi.org/10.1016/j.jms.2017.11.007}{doi:10.1016/j.jms.2017.11.007}, V. Van, J. Bruikhuisen, W. Stahl, V. Illyushin, H. V. L. Nguyen, \textit{J. Mol. Spectrosc.} \textbf{343}, 121-125 (2018).} and 356.5 cm$^{-1}$ for \textit{syn}-2-acetyl-5-methylfuran.\footnote{\href{https://dx.doi.org/10.1002/cphc.201600757}{doi:10.1002/cphc.201600757}, V. Van, W. Stahl, H. V. L. Nguyen, \textit{Chem. Phys. Chem.} \textbf{17}, 3223-3228 (2016).} The methyl torsional barrier of 2-methylfuran derivates is tuned by the same manner as it is for the thiophene analogues. For 2MTP and 2Cl5MTP, we used a state-of-the-art pulsed molecular jet Fourier transform spectrometer to measure the microwave spectra in the frequency range of 2-26.5 GHz. The spectra of the $^{34}$S and $^{13}$C isotopologues of 2MTP could be observed in natural abundances and the semi-experimental $r_\mathrm{e}^{\mathrm{SE}}$ structure was determined. for 2Cl5MTP, the $^{35}$Cl and $^{37}$Cl nuclei give rise to a nuclear quadrupole hyperfine structure in the spectrum in addition to the A-E torsional splittings of the methyl internal rotation.

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