Real-space observation of the dissociation of a transition metal complex and its concurrent energy redistribution
Mechanistic insights into photodissociation dynamics of transition metal carbonyls, like Fe(CO)<sub>5</sub>, are fundamental for understanding active catalytic intermediates. Although extensively studied, the structural dynamics of these systems remain elusive. Using ultrafast X-ray scattering, we uncover the photochemistry of Fe(CO)<sub>5</sub> in real space and time, observing synchronous oscillations in atomic pair distances, followed by a prompt rotating CO release preferentially in the axial direction. This behavior aligns with simulations, reflecting the interplay between the axial Fe-C distances' potential energy landscape and non-adiabatic transitions between metal-to-ligand charge-transfer states. Additionally, we characterize a secondary delayed CO release associated with a reduction of Fe-C steady state distances and structural dynamics of the formed Fe(CO)<sub>4</sub>. Our results quantify energy redistribution across vibration, rotation, and translation degrees of freedom, offering a microscopic view of complex structural dynamics, enhancing our grasp on Fe(CO)<sub>5</sub> photodissociation, and advancing our understanding of transition metal catalytic systems.
Authors
- Michael Odelius (ORCID: https://orcid.org/0000-0002-7023-2486)
- Sergio Carbajo (ORCID: https://orcid.org/0000-0002-5292-4470)
- Sébastien Boutet (ORCID: https://orcid.org/0000-0003-3928-1244)
- Brian Stankus (ORCID: https://orcid.org/0000-0002-1351-1286)
- Adi Natan (ORCID: https://orcid.org/0000-0002-6594-7794)
- Jennifer M. Ruddock (ORCID: https://orcid.org/0000-0002-5457-4443)
- Thomas J. Lane (ORCID: https://orcid.org/0000-0003-2627-4432)
- P. H. Bucksbaum (ORCID: https://orcid.org/0000-0003-1258-5571)
- S. Nelson (ORCID: https://orcid.org/0000-0002-2937-6074)
- Ambar Banerjee (ORCID: https://orcid.org/0000-0001-6113-7033)
- Elisa Biasin (ORCID: https://orcid.org/0000-0002-7276-4224)
- Kelly J. Gaffney (ORCID: https://orcid.org/0000-0002-0525-6465)
- A. Schori (ORCID: https://orcid.org/0000-0002-8314-6958)
- Michael P. Minitti (ORCID: https://orcid.org/0000-0002-9854-9717)
- Jason E. Koglin (ORCID: https://orcid.org/0000-0001-6811-6083)
- Peter Weber (ORCID: https://orcid.org/0000-0001-6022-6050)
- Frédéric Poitevin (ORCID: https://orcid.org/0000-0002-3181-8652)
- Andreas Kaldun (ORCID: https://orcid.org/0000-0003-2734-5589)
- Robert M. Parrish (ORCID: https://orcid.org/0000-0002-2406-4741)
- Thomas Wolf (ORCID: https://orcid.org/0000-0002-0641-1279)
- Kathryn Ledbetter (ORCID: https://orcid.org/0000-0002-3961-8524)
- Kristjan Kunnus (ORCID: https://orcid.org/0000-0002-9777-2685)
- Mengning Liang (ORCID: https://orcid.org/0009-0003-6711-4555)
- James M. Glownia
- Jordan T. O’Neal
- Robert J. Hartsock
Institutions
- Pacific Northwest National Laboratory (US)
- Stockholm University (SE)
- Western Connecticut State University (US)
- Brown University (US)
- SLAC National Accelerator Laboratory (US)
- Linac Coherent Light Source (US)
- TCG Crest (IN)
- Stanford University (US)
Publication Details
- Journal
- Nature Communications
- Published
- 2025-05-22
- DOI
- https://doi.org/10.1038/s41467-025-60009-8
- Citations
- 1
- Primary Topic
- Advanced Chemical Physics Studies
- Type
- article
- Field-Weighted Citation Impact
- 1.25
Funders
- U.S. Department of Energy
- Vetenskapsrådet
- Office of Science
- Basic Energy Sciences
- Chemical Sciences, Geosciences, and Biosciences Division
- SLAC National Accelerator Laboratory