Journal article

Publication year: 2021

Pages: 6732-6739

Journal: Chemistry - A European Journal

Volume number: 27

Issue number: 22

ISSN: 0947-6539

Open access status: Green

DOI Link: https://doi.org/10.1002/chem.202005188

Publisher: Wiley

Abstract: 
As sulfur-containing organic molecules thioamides and their isomers are conceivable intermediates in prebiotic chemistry, for example, in the formation of amino acids and thiazoles and resemble viable candidates for detection in interstellar media. Here, we report the characterization of parent thioformamide in the solid state via single-crystal X-ray diffraction and its photochemical interconversion to its hitherto unreported higher energy tautomer thiolimine in inert argon and dinitrogen matrices. Upon photogeneration, four conformers of thiolimine form, whose ratio depends on the employed wavelength. One of these conformers interconverts due to quantum mechanical tunneling with a half-life of 30-45 min in both matrix materials at 3 and 20 K. A spontaneous reverse reaction from thiolimine to thioformamide is not observed. To support our experimental findings, we explored the potential energy surface of the system at the AE-CCSD(T)/aug-cc-pCVTZ level of theory and computed tunneling half-lives with the CVT/SCT approach applying DFT methods.

Harvard Citation style: Bernhardt, B., Dressler, F., Eckhardt, A., Becker, J. and Schreiner, P. (2021) Characterization of the Simplest Thiolimine: The Higher Energy Tautomer of Thioformamide, Chemistry - A European Journal, 27(22), pp. 6732-6739. https://doi.org/10.1002/chem.202005188

APA Citation style: Bernhardt, B., Dressler, F., Eckhardt, A., Becker, J., & Schreiner, P. (2021). Characterization of the Simplest Thiolimine: The Higher Energy Tautomer of Thioformamide. Chemistry - A European Journal. 27(22), 6732-6739. https://doi.org/10.1002/chem.202005188