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

Autor: Köck EM; Institute of Physical Chemistry, University of Innsbruck, Innrain 52c, 6020, Innsbruck, Austria.; Max-Planck-Institut für Chemische Energiekonversion, Stiftstraße 34-36, 45470, Mülheim an der Ruhr, Germany., Bernard J; Institute of Physical Chemistry, University of Innsbruck, Innrain 52c, 6020, Innsbruck, Austria.; Max-Planck-Institut für Chemische Energiekonversion, Stiftstraße 34-36, 45470, Mülheim an der Ruhr, Germany., Podewitz M; Institute of General, Inorganic and Theoretical Chemistry, University of Innsbruck, Innrain 80-82, 6020, Innsbruck, Austria., Dinu DF; Institute of General, Inorganic and Theoretical Chemistry, University of Innsbruck, Innrain 80-82, 6020, Innsbruck, Austria., Huber RG; Institute of General, Inorganic and Theoretical Chemistry, University of Innsbruck, Innrain 80-82, 6020, Innsbruck, Austria., Liedl KR; Institute of General, Inorganic and Theoretical Chemistry, University of Innsbruck, Innrain 80-82, 6020, Innsbruck, Austria., Grothe H; Institute of Materials Chemistry, TU Wien, Getreidemarkt 9/165, 1060, Vienna, Austria., Bertel E; Institute of Physical Chemistry, University of Innsbruck, Innrain 52c, 6020, Innsbruck, Austria., Schlögl R; Max-Planck-Institut für Chemische Energiekonversion, Stiftstraße 34-36, 45470, Mülheim an der Ruhr, Germany., Loerting T; Institute of Physical Chemistry, University of Innsbruck, Innrain 52c, 6020, Innsbruck, Austria.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2020 Jan 02; Vol. 26 (1), pp. 285-305. Date of Electronic Publication: 2019 Nov 26.
DOI: 10.1002/chem.201904142
Abstrakt: In this work, earlier studies reporting α-H 2 CO 3 are revised. The cryo-technique pioneered by Hage, Hallbrucker, and Mayer (HHM) is adapted to supposedly prepare carbonic acid from KHCO 3 . In methanolic solution, methylation of the salt is found, which upon acidification transforms to the monomethyl ester of carbonic acid (CAME, HO-CO-OCH 3 ). 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 CH 3 - groups as well as 12 C and 13 C 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 .
(© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)
Databáze: MEDLINE
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