Alpha‐Carbonic Acid Revisited: Carbonic Acid Monomethyl Ester as a Solid and its Conformational Isomerism in the Gas Phase
Abstract 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 th...
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crwiley:10.1002/chem.201904142 2024-06-23T07:52:02+00:00 Alpha‐Carbonic Acid Revisited: Carbonic Acid Monomethyl Ester as a Solid and its Conformational Isomerism in the Gas Phase Köck, Eva‐Maria Bernard, Jürgen Podewitz, Maren Dinu, Dennis F. Huber, Roland G. Liedl, Klaus R. Grothe, Hinrich Bertel, Erminald Schlögl, Robert Loerting, Thomas Austrian Science Fund 2019 http://dx.doi.org/10.1002/chem.201904142 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fchem.201904142 https://onlinelibrary.wiley.com/doi/pdf/10.1002/chem.201904142 https://onlinelibrary.wiley.com/doi/full-xml/10.1002/chem.201904142 en eng Wiley http://creativecommons.org/licenses/by/4.0/ Chemistry – A European Journal volume 26, issue 1, page 285-305 ISSN 0947-6539 1521-3765 journal-article 2019 crwiley https://doi.org/10.1002/chem.201904142 2024-06-13T04:21:30Z Abstract 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 . Article in Journal/Newspaper Carbonic acid Wiley Online Library Chemistry – A European Journal 26 1 285 305 |
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English |
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Abstract 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 . |
author2 |
Austrian Science Fund |
format |
Article in Journal/Newspaper |
author |
Köck, Eva‐Maria Bernard, Jürgen Podewitz, Maren Dinu, Dennis F. Huber, Roland G. Liedl, Klaus R. Grothe, Hinrich Bertel, Erminald Schlögl, Robert Loerting, Thomas |
spellingShingle |
Köck, Eva‐Maria Bernard, Jürgen Podewitz, Maren Dinu, Dennis F. Huber, Roland G. Liedl, Klaus R. Grothe, Hinrich Bertel, Erminald Schlögl, Robert Loerting, Thomas Alpha‐Carbonic Acid Revisited: Carbonic Acid Monomethyl Ester as a Solid and its Conformational Isomerism in the Gas Phase |
author_facet |
Köck, Eva‐Maria Bernard, Jürgen Podewitz, Maren Dinu, Dennis F. Huber, Roland G. Liedl, Klaus R. Grothe, Hinrich Bertel, Erminald Schlögl, Robert Loerting, Thomas |
author_sort |
Köck, Eva‐Maria |
title |
Alpha‐Carbonic Acid Revisited: Carbonic Acid Monomethyl Ester as a Solid and its Conformational Isomerism in the Gas Phase |
title_short |
Alpha‐Carbonic Acid Revisited: Carbonic Acid Monomethyl Ester as a Solid and its Conformational Isomerism in the Gas Phase |
title_full |
Alpha‐Carbonic Acid Revisited: Carbonic Acid Monomethyl Ester as a Solid and its Conformational Isomerism in the Gas Phase |
title_fullStr |
Alpha‐Carbonic Acid Revisited: Carbonic Acid Monomethyl Ester as a Solid and its Conformational Isomerism in the Gas Phase |
title_full_unstemmed |
Alpha‐Carbonic Acid Revisited: Carbonic Acid Monomethyl Ester as a Solid and its Conformational Isomerism in the Gas Phase |
title_sort |
alpha‐carbonic acid revisited: carbonic acid monomethyl ester as a solid and its conformational isomerism in the gas phase |
publisher |
Wiley |
publishDate |
2019 |
url |
http://dx.doi.org/10.1002/chem.201904142 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fchem.201904142 https://onlinelibrary.wiley.com/doi/pdf/10.1002/chem.201904142 https://onlinelibrary.wiley.com/doi/full-xml/10.1002/chem.201904142 |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_source |
Chemistry – A European Journal volume 26, issue 1, page 285-305 ISSN 0947-6539 1521-3765 |
op_rights |
http://creativecommons.org/licenses/by/4.0/ |
op_doi |
https://doi.org/10.1002/chem.201904142 |
container_title |
Chemistry – A European Journal |
container_volume |
26 |
container_issue |
1 |
container_start_page |
285 |
op_container_end_page |
305 |
_version_ |
1802643238040895488 |