Journal article

Publication year: 2017

Pages: 439-445

Journal: Journal of Analytical and Applied Pyrolysis

Volume number: 124

ISSN: 0165-2370

DOI Link: https://doi.org/10.1016/j.jaap.2017.02.024

Publisher: Elsevier

Abstract: 

Carbonothioic O,O-acid (monothiocarbonic acid), the sulfur analogue of carbonic acid, is thus far an experimentally unreported molecule of atmospheric and biochemical relevance. Computations at the CCSD(T)/cc-pVQZ//CCSD(T)/cc-pVTZ level of theory reveal that its carbonothioic O,S-acid tautomer is energetically favored over the carbonothioic O,O-acid tautomer and that the decomposition of the former to H2S and CO2 is prevented by a barrier in excess of 30 kcal mol(-1). Therefore, we attempted to prepare carbonothioic-O,O-acid under matrix isolation conditions via high vacuum flash pyrolysis (HVFP) of O,S-di-tert-butyl carbonothioate in analogy to the previously reported successful preparation of carbonic acid. Pyrolysis at 900 degrees C only produced isobutene, CO2, and tert-buthylthiol, while S-tert-butyl O-hydrogen carbonothioate is the most likely additional product identifiable at 690 degrees C pyrolysis temperature. Density functional theory computations at the M06-2X/cc-pVTZ level were used to understand the pyrolysis pathways and help determine the leaving group ability in the ester pyrolysis step, and our inability to observe the carbonothioic acids via our chosen pyrolysis path. (C) 2017 Elsevier B.V. All rights reserved.

Harvard Citation style: Niedek, D., Wagner, P. and Schreiner, P. (2017) Towards the pyrolytic preparation of carbonothioic O,O-acid (monothiocarbonic acid), Journal of Analytical and Applied Pyrolysis, 124, pp. 439-445. https://doi.org/10.1016/j.jaap.2017.02.024

APA Citation style: Niedek, D., Wagner, P., & Schreiner, P. (2017). Towards the pyrolytic preparation of carbonothioic O,O-acid (monothiocarbonic acid). Journal of Analytical and Applied Pyrolysis. 124, 439-445. https://doi.org/10.1016/j.jaap.2017.02.024