Real-space observation of the dissociation of a transition metal complex and its concurrent energy redistribution
- Aviad Schori
- Elisa Biasin
- Ambar Banerjee
- Sébastien Boutet
- Philip H. Bucksbaum
- Sergio Carbajo
- Kelly J. Gaffney
- James M. Glownia
- Robert Hartsock
- Kathryn Ledbetter
- Andreas Kaldun
- Jason E. Koglin
- Kristjan Kunnus
- Thomas J. Lane
- Mengning Liang
- Michael P. Minitti
- Jordan T. O’Neal
- Robert M. Parrish
- Frédéric Poitevin
- Jennifer M. Ruddock
- Silke Nelson
- Brian Stankus
- Peter M. Weber
- Thomas J. A. Wolf
- Michael Odelius
- Adi Natan
2025-05-22
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.