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Photoinduced bond oscillations in ironpentacarbonyl give delayed synchronous bursts of carbonmonoxide release.
- Source :
-
Nature communications [Nat Commun] 2022 Mar 14; Vol. 13 (1), pp. 1337. Date of Electronic Publication: 2022 Mar 14. - Publication Year :
- 2022
-
Abstract
- 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) <subscript>5</subscript> 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) <subscript>5</subscript> 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 <superscript>*</superscript> (Fe-C) anti-bonding character of the receiving orbital in the dissociative MC states.<br /> (© 2022. The Author(s).)
- Subjects :
- Ligands
Metals chemistry
Transition Elements
Subjects
Details
- Language :
- English
- ISSN :
- 2041-1723
- Volume :
- 13
- Issue :
- 1
- Database :
- MEDLINE
- Journal :
- Nature communications
- Publication Type :
- Academic Journal
- Accession number :
- 35288563
- Full Text :
- https://doi.org/10.1038/s41467-022-28997-z