Real-space observation of the dissociation of a transition metal complex and its concurrent energy redistribution

Year: 2025

Type: article

Abstract: Mechanistic insights into photodissociation dynamics of transition metal carbonyls, like Fe(CO)5, 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)5 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)4. 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)5 photodissociation, and advancing our understanding of transition metal catalytic systems.

Source: Nature Communications

DOI: 10.1038/s41467-025-60009-8

Institutions: SLAC National Accelerator Laboratory, Pacific Northwest National Laboratory, Stockholm University, TCG Crest, Linac Coherent Light Source, Stanford University, Brown University, Western Connecticut State University

Language: English

Topic: X-ray Spectroscopy and Fluorescence Analysis

Subfield: Radiation

Field: Physics and Astronomy

Domain: Physical Sciences

Open Access status: gold

Estimated APC paid: $6,990

Funders: U.S. Department of Energy, Vetenskapsrådet, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, SLAC National Accelerator Laboratory

OpenAlex ID: W4410590318