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  Alpha-Carbonic Acid Revisited: Carbonic Acid Monomethyl Ester as a Solid and its Conformational Isomerism in the Gas Phase

Köck, E.-M., Bernard, J., Podewitz, M., Dinu, D. F., Huber, R. G., Liedl, K. R., et al. (2020). Alpha-Carbonic Acid Revisited: Carbonic Acid Monomethyl Ester as a Solid and its Conformational Isomerism in the Gas Phase. Chemistry – A European Journal, 26(1), 285-305. doi:10.1002/chem.201904142.

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Item Permalink: http://hdl.handle.net/21.11116/0000-0006-5A95-D Version Permalink: http://hdl.handle.net/21.11116/0000-0006-5A96-C
Genre: Journal Article

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 Creators:
Köck, Eva-Maria1, Author              
Bernard, Jürgen1, Author              
Podewitz, Maren, Author
Dinu, Dennis F., Author
Huber, Roland G., Author
Liedl, Klaus R., Author
Grothe, Hinrich, Author
Bertel, Erminald, Author
Schlögl, Robert1, Author              
Loerting, Thomas, Author
Affiliations:
1Research Department Schlögl, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023874              

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 Abstract: In this work, earlier studies reporting alpha-H2CO3 are revised. The cryo-technique pioneered by Hage, Hallbrucker, and Mayer (HHM) is adapted to supposedly prepare carbonic acid from KHCO3. In methanolic solution, methylation of the salt is found, which upon acidification transforms to the monomethyl ester of carbonic acid (CAME, HO-CO-OCH3). Infrared spectroscopy data both of the solid at 210 K and of the evaporated molecules trapped and isolated in argon matrix at 10 K are presented. The interpretation of the observed bands on the basis of carbonic acid [as suggested originally by HHM in their publications from 1993-1997 and taken over by Winkel et al., J. Am. Chem. Soc. 2007 and Bernard et al., Angew. Chem. Int. Ed. 2011] is inferior compared with the interpretation on the basis of CAME. The assignment relies on isotope substitution experiments, including deuteration of the OH- and CH3- groups as well as C-12 and C-13 isotope exchange and on variation of the solvents in both preparation steps. The interpretation of the single molecule spectroscopy experiments is aided by a comprehensive calculation of high-level ab initio frequencies for gas-phase molecules and clusters in the harmonic approximation. This analysis provides evidence for the existence of not only single CAME molecules but also CAME dimers and water complexes in the argon matrix. Furthermore, different conformational CAME isomers are identified, where conformational isomerism is triggered in experiments through UV irradiation. In contrast to earlier studies, this analysis allows explanation of almost every single band of the complex spectra in the range between 4000 and 600 cm(-1).

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Language(s): eng - English
 Dates: 2020
 Publication Status: Published in print
 Pages: -
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: ISI: 000498477800001
DOI: 10.1002/chem.201904142
 Degree: -

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Title: Chemistry – A European Journal
  Other : Chem. – Eur. J.
  Other : Chem. Eur. J.
Source Genre: Journal
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Publ. Info: Weinheim : Wiley-VCH
Pages: - Volume / Issue: 26 (1) Sequence Number: - Start / End Page: 285 - 305 Identifier: ISSN: 0947-6539
CoNE: https://pure.mpg.de/cone/journals/resource/954926979058