Journal article

Authors list: Bernhardt, B; Schauermann, M; Solel, E; Eckhardt, AK; Schreiner, PR

Publication year: 2022

Pages: 130-135

Journal: Chemical Science

Volume number: 14

Issue number: 1

ISSN: 2041-6520

eISSN: 2041-6539

Open access status: Gold

DOI Link: https://doi.org/10.1039/d2sc05388h

Publisher: Royal Society of Chemistry

Abstract: 
The search for methods to bind CO2 and use it synthetically as a C-1-building block under mild conditions is an ongoing endeavor of great urgency. The formation of heterocyclic carbene-carbon dioxide adducts occurs rapidly when the carbene is generated in solution in the presence of CO2. Here we demonstrate the reversible formation of a complex of the hitherto unreported aminomercaptocarbene (H2N-C''-SH) with CO2 isolated in solid argon by photolysis of 2-amino-2-thioxoacetic acid. Remarkably, the complex disappears in the dark as deduced by time-dependent matrix infrared measurements, and equilibrates back to the covalently bound starting material. This kinetically excluded process below ca. 8 K is made possible through heavy-atom quantum mechanical tunneling, as also evident from density functional theory and ab initio computations at the CCSD(T)/cc-pVTZ level of theory. Our results provide insight into CO2 activation using a carbene and emphasize the role of quantum mechanical tunneling in organic processes, even involving heavy atoms.

Harvard Citation style: Bernhardt, B., Schauermann, M., Solel, E., Eckhardt, A. and Schreiner, P. (2022) Equilibrating parent aminomercaptocarbene and CO2 with 2-amino-2-thioxoacetic acid via heavy-atom quantum tunneling, Chemical Science, 14(1), pp. 130-135. https://doi.org/10.1039/d2sc05388h

APA Citation style: Bernhardt, B., Schauermann, M., Solel, E., Eckhardt, A., & Schreiner, P. (2022). Equilibrating parent aminomercaptocarbene and CO2 with 2-amino-2-thioxoacetic acid via heavy-atom quantum tunneling. Chemical Science. 14(1), 130-135. https://doi.org/10.1039/d2sc05388h