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Cluster size dependent coordination of formate to free manganese oxide clusters
The interaction of free manganese oxide clusters, Mn(x)O(y)(+) (x = 1–9, y = 0–12), with formic acid was studied via infrared multiple-photon dissociation (IR-MPD) spectroscopy together with calculations using density functional theory (DFT). Clusters containing only one Mn atom, such as MnO(2)(+) a...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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The Royal Society of Chemistry
2023
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10686260/ https://www.ncbi.nlm.nih.gov/pubmed/37986571 http://dx.doi.org/10.1039/d3cp04035f |
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author | Lang, Sandra M. Bernhardt, Thorsten M. Bakker, Joost M. Barnett, Robert N. Landman, Uzi |
author_facet | Lang, Sandra M. Bernhardt, Thorsten M. Bakker, Joost M. Barnett, Robert N. Landman, Uzi |
author_sort | Lang, Sandra M. |
collection | PubMed |
description | The interaction of free manganese oxide clusters, Mn(x)O(y)(+) (x = 1–9, y = 0–12), with formic acid was studied via infrared multiple-photon dissociation (IR-MPD) spectroscopy together with calculations using density functional theory (DFT). Clusters containing only one Mn atom, such as MnO(2)(+) and MnO(4)(+), bind formic acid as an intact molecule in both the cis- and trans-configuration. In contrast, all clusters containing two or more manganese atoms deprotonate the acid's hydroxyl group. The coordination of the resulting formate group is strongly cluster-size-dependent according to supporting DFT calculations for selected model systems. For Mn(2)O(2)(+) the co-existence of two isomers with the formate bound in a bidentate bridging and chelating configurations, respectively, is found, whereas for Mn(2)O(4)(+) the bidentate chelating configuration is preferred. In contrast, the bidentate bridging structure is energetically considerably more favorable for Mn(4)O(4)(+). This binding motif stabilizes the 2D ring structure of the core of the Mn(4)O(4)(+) cluster with respect to the 3D cubic geometry of the Mn(4)O(4)(+) cluster core. |
format | Online Article Text |
id | pubmed-10686260 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-106862602023-11-30 Cluster size dependent coordination of formate to free manganese oxide clusters Lang, Sandra M. Bernhardt, Thorsten M. Bakker, Joost M. Barnett, Robert N. Landman, Uzi Phys Chem Chem Phys Chemistry The interaction of free manganese oxide clusters, Mn(x)O(y)(+) (x = 1–9, y = 0–12), with formic acid was studied via infrared multiple-photon dissociation (IR-MPD) spectroscopy together with calculations using density functional theory (DFT). Clusters containing only one Mn atom, such as MnO(2)(+) and MnO(4)(+), bind formic acid as an intact molecule in both the cis- and trans-configuration. In contrast, all clusters containing two or more manganese atoms deprotonate the acid's hydroxyl group. The coordination of the resulting formate group is strongly cluster-size-dependent according to supporting DFT calculations for selected model systems. For Mn(2)O(2)(+) the co-existence of two isomers with the formate bound in a bidentate bridging and chelating configurations, respectively, is found, whereas for Mn(2)O(4)(+) the bidentate chelating configuration is preferred. In contrast, the bidentate bridging structure is energetically considerably more favorable for Mn(4)O(4)(+). This binding motif stabilizes the 2D ring structure of the core of the Mn(4)O(4)(+) cluster with respect to the 3D cubic geometry of the Mn(4)O(4)(+) cluster core. The Royal Society of Chemistry 2023-11-14 /pmc/articles/PMC10686260/ /pubmed/37986571 http://dx.doi.org/10.1039/d3cp04035f Text en This journal is © the Owner Societies https://creativecommons.org/licenses/by/3.0/ |
spellingShingle | Chemistry Lang, Sandra M. Bernhardt, Thorsten M. Bakker, Joost M. Barnett, Robert N. Landman, Uzi Cluster size dependent coordination of formate to free manganese oxide clusters |
title | Cluster size dependent coordination of formate to free manganese oxide clusters |
title_full | Cluster size dependent coordination of formate to free manganese oxide clusters |
title_fullStr | Cluster size dependent coordination of formate to free manganese oxide clusters |
title_full_unstemmed | Cluster size dependent coordination of formate to free manganese oxide clusters |
title_short | Cluster size dependent coordination of formate to free manganese oxide clusters |
title_sort | cluster size dependent coordination of formate to free manganese oxide clusters |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10686260/ https://www.ncbi.nlm.nih.gov/pubmed/37986571 http://dx.doi.org/10.1039/d3cp04035f |
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