Real-space observation of the dissociation of a transition metal complex and its concurrent energy redistribution
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 unc...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2025-05-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-60009-8 |
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| author | 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 |
| author_facet | 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 |
| author_sort | Aviad Schori |
| collection | DOAJ |
| description | 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. |
| format | Article |
| id | doaj-art-bf07a6caf0654615ac05508d25fe43fd |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-05-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-bf07a6caf0654615ac05508d25fe43fd2025-08-20T03:48:15ZengNature PortfolioNature Communications2041-17232025-05-011611910.1038/s41467-025-60009-8Real-space observation of the dissociation of a transition metal complex and its concurrent energy redistributionAviad Schori0Elisa Biasin1Ambar Banerjee2Sébastien Boutet3Philip H. Bucksbaum4Sergio Carbajo5Kelly J. Gaffney6James M. Glownia7Robert Hartsock8Kathryn Ledbetter9Andreas Kaldun10Jason E. Koglin11Kristjan Kunnus12Thomas J. Lane13Mengning Liang14Michael P. Minitti15Jordan T. O’Neal16Robert M. Parrish17Frédéric Poitevin18Jennifer M. Ruddock19Silke Nelson20Brian Stankus21Peter M. Weber22Thomas J. A. Wolf23Michael Odelius24Adi Natan25Stanford PULSE Institute, SLAC National Accelerator LaboratoryStanford PULSE Institute, SLAC National Accelerator LaboratoryDepartment of Physics, Stockholm UniversityLinac Coherent Light Source, SLAC National Accelerator LaboratoryStanford PULSE Institute, SLAC National Accelerator LaboratoryLinac Coherent Light Source, SLAC National Accelerator LaboratoryStanford PULSE Institute, SLAC National Accelerator LaboratoryLinac Coherent Light Source, SLAC National Accelerator LaboratoryStanford PULSE Institute, SLAC National Accelerator LaboratoryStanford PULSE Institute, SLAC National Accelerator LaboratoryStanford PULSE Institute, SLAC National Accelerator LaboratoryLinac Coherent Light Source, SLAC National Accelerator LaboratoryStanford PULSE Institute, SLAC National Accelerator LaboratoryLinac Coherent Light Source, SLAC National Accelerator LaboratoryLinac Coherent Light Source, SLAC National Accelerator LaboratoryLinac Coherent Light Source, SLAC National Accelerator LaboratoryStanford PULSE Institute, SLAC National Accelerator LaboratoryStanford PULSE Institute, SLAC National Accelerator LaboratoryStanford PULSE Institute, SLAC National Accelerator LaboratoryDepartment of Chemistry, Brown UniversityLinac Coherent Light Source, SLAC National Accelerator LaboratoryDepartment of Chemistry, Brown UniversityDepartment of Chemistry, Brown UniversityStanford PULSE Institute, SLAC National Accelerator LaboratoryDepartment of Physics, Stockholm UniversityStanford PULSE Institute, SLAC National Accelerator LaboratoryAbstract 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.https://doi.org/10.1038/s41467-025-60009-8 |
| spellingShingle | 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 Real-space observation of the dissociation of a transition metal complex and its concurrent energy redistribution Nature Communications |
| title | Real-space observation of the dissociation of a transition metal complex and its concurrent energy redistribution |
| title_full | Real-space observation of the dissociation of a transition metal complex and its concurrent energy redistribution |
| title_fullStr | Real-space observation of the dissociation of a transition metal complex and its concurrent energy redistribution |
| title_full_unstemmed | Real-space observation of the dissociation of a transition metal complex and its concurrent energy redistribution |
| title_short | Real-space observation of the dissociation of a transition metal complex and its concurrent energy redistribution |
| title_sort | real space observation of the dissociation of a transition metal complex and its concurrent energy redistribution |
| url | https://doi.org/10.1038/s41467-025-60009-8 |
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