TY - JOUR
T1 - Real-space observation of the dissociation of a transition metal complex and its concurrent energy redistribution
AU - Schori, Aviad
AU - Biasin, Elisa
AU - Banerjee, Ambar
AU - Boutet, Sébastien
AU - Bucksbaum, Philip H.
AU - Carbajo, Sergio
AU - Gaffney, Kelly J.
AU - Glownia, James M.
AU - Hartsock, Robert
AU - Ledbetter, Kathryn
AU - Kaldun, Andreas
AU - Koglin, Jason E.
AU - Kunnus, Kristjan
AU - Lane, Thomas J.
AU - Liang, Mengning
AU - Minitti, Michael P.
AU - O’Neal, Jordan T.
AU - Parrish, Robert M.
AU - Poitevin, Frédéric
AU - Ruddock, Jennifer M.
AU - Nelson, Silke
AU - Stankus, Brian
AU - Weber, Peter M.
AU - Wolf, Thomas J.A.
AU - Odelius, Michael
AU - Natan, Adi
N1 - Publisher Copyright:
© The Author(s) 2025.
PY - 2025/5/22
Y1 - 2025/5/22
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=105005779287&partnerID=8YFLogxK
U2 - 10.1038/s41467-025-60009-8
DO - 10.1038/s41467-025-60009-8
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C2 - 40404642
AN - SCOPUS:105005779287
SN - 2041-1723
VL - 16
JO - Nature Communications
JF - Nature Communications
IS - 1
M1 - 4767
ER -