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Photoinduced bond oscillations in ironpentacarbonyl give delayed synchronous bursts of carbonmonoxide release
Early excited state dynamics in the photodissociation of transition metal carbonyls determines the chemical nature of short-lived catalytically active reaction intermediates. However, time-resolved experiments have not yet revealed mechanistic details in the sub-picosecond regime. Hence, in this stu...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8921231/ https://www.ncbi.nlm.nih.gov/pubmed/35288563 http://dx.doi.org/10.1038/s41467-022-28997-z |
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author | Banerjee, Ambar Coates, Michael R. Kowalewski, Markus Wikmark, Hampus Jay, Raphael M. Wernet, Philippe Odelius, Michael |
author_facet | Banerjee, Ambar Coates, Michael R. Kowalewski, Markus Wikmark, Hampus Jay, Raphael M. Wernet, Philippe Odelius, Michael |
author_sort | Banerjee, Ambar |
collection | PubMed |
description | Early excited state dynamics in the photodissociation of transition metal carbonyls determines the chemical nature of short-lived catalytically active reaction intermediates. However, time-resolved experiments have not yet revealed mechanistic details in the sub-picosecond regime. Hence, in this study the photoexcitation of ironpentacarbonyl Fe(CO)(5) is simulated with semi-classical excited state molecular dynamics. We find that the bright metal-to-ligand charge-transfer (MLCT) transition induces synchronous Fe-C oscillations in the trigonal bipyramidal complex leading to periodically reoccurring release of predominantly axial CO. Metaphorically the photoactivated Fe(CO)(5) acts as a CO geyser, as a result of dynamics in the potential energy landscape of the axial Fe-C distances and non-adiabatic transitions between manifolds of bound MLCT and dissociative metal-centered (MC) excited states. The predominant release of axial CO ligands and delayed release of equatorial CO ligands are explained in a unified mechanism based on the σ(*)(Fe-C) anti-bonding character of the receiving orbital in the dissociative MC states. |
format | Online Article Text |
id | pubmed-8921231 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-89212312022-04-01 Photoinduced bond oscillations in ironpentacarbonyl give delayed synchronous bursts of carbonmonoxide release Banerjee, Ambar Coates, Michael R. Kowalewski, Markus Wikmark, Hampus Jay, Raphael M. Wernet, Philippe Odelius, Michael Nat Commun Article Early excited state dynamics in the photodissociation of transition metal carbonyls determines the chemical nature of short-lived catalytically active reaction intermediates. However, time-resolved experiments have not yet revealed mechanistic details in the sub-picosecond regime. Hence, in this study the photoexcitation of ironpentacarbonyl Fe(CO)(5) is simulated with semi-classical excited state molecular dynamics. We find that the bright metal-to-ligand charge-transfer (MLCT) transition induces synchronous Fe-C oscillations in the trigonal bipyramidal complex leading to periodically reoccurring release of predominantly axial CO. Metaphorically the photoactivated Fe(CO)(5) acts as a CO geyser, as a result of dynamics in the potential energy landscape of the axial Fe-C distances and non-adiabatic transitions between manifolds of bound MLCT and dissociative metal-centered (MC) excited states. The predominant release of axial CO ligands and delayed release of equatorial CO ligands are explained in a unified mechanism based on the σ(*)(Fe-C) anti-bonding character of the receiving orbital in the dissociative MC states. Nature Publishing Group UK 2022-03-14 /pmc/articles/PMC8921231/ /pubmed/35288563 http://dx.doi.org/10.1038/s41467-022-28997-z Text en © The Author(s) 2022 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) . |
spellingShingle | Article Banerjee, Ambar Coates, Michael R. Kowalewski, Markus Wikmark, Hampus Jay, Raphael M. Wernet, Philippe Odelius, Michael Photoinduced bond oscillations in ironpentacarbonyl give delayed synchronous bursts of carbonmonoxide release |
title | Photoinduced bond oscillations in ironpentacarbonyl give delayed synchronous bursts of carbonmonoxide release |
title_full | Photoinduced bond oscillations in ironpentacarbonyl give delayed synchronous bursts of carbonmonoxide release |
title_fullStr | Photoinduced bond oscillations in ironpentacarbonyl give delayed synchronous bursts of carbonmonoxide release |
title_full_unstemmed | Photoinduced bond oscillations in ironpentacarbonyl give delayed synchronous bursts of carbonmonoxide release |
title_short | Photoinduced bond oscillations in ironpentacarbonyl give delayed synchronous bursts of carbonmonoxide release |
title_sort | photoinduced bond oscillations in ironpentacarbonyl give delayed synchronous bursts of carbonmonoxide release |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8921231/ https://www.ncbi.nlm.nih.gov/pubmed/35288563 http://dx.doi.org/10.1038/s41467-022-28997-z |
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