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Photoinduced bond oscillations in ironpentacarbonyl give delayed synchronous bursts of carbonmonoxide release

Author

Listed:
  • Ambar Banerjee

    (Stockholm University, AlbaNova University Center)

  • Michael R. Coates

    (Stockholm University, AlbaNova University Center)

  • Markus Kowalewski

    (Stockholm University, AlbaNova University Center)

  • Hampus Wikmark

    (Uppsala University)

  • Raphael M. Jay

    (Uppsala University)

  • Philippe Wernet

    (Uppsala University)

  • Michael Odelius

    (Stockholm University, AlbaNova University Center)

Abstract

Early excited state dynamics in the photodissociation of transition metal carbonyls determines the chemical nature of short-lived catalytically active reaction intermediates. However, time-resolved experiments have not yet revealed mechanistic details in the sub-picosecond regime. Hence, in this study the photoexcitation of ironpentacarbonyl Fe(CO)5 is simulated with semi-classical excited state molecular dynamics. We find that the bright metal-to-ligand charge-transfer (MLCT) transition induces synchronous Fe-C oscillations in the trigonal bipyramidal complex leading to periodically reoccurring release of predominantly axial CO. Metaphorically the photoactivated Fe(CO)5 acts as a CO geyser, as a result of dynamics in the potential energy landscape of the axial Fe-C distances and non-adiabatic transitions between manifolds of bound MLCT and dissociative metal-centered (MC) excited states. The predominant release of axial CO ligands and delayed release of equatorial CO ligands are explained in a unified mechanism based on the σ*(Fe-C) anti-bonding character of the receiving orbital in the dissociative MC states.

Suggested Citation

  • Ambar Banerjee & Michael R. Coates & Markus Kowalewski & Hampus Wikmark & Raphael M. Jay & Philippe Wernet & Michael Odelius, 2022. "Photoinduced bond oscillations in ironpentacarbonyl give delayed synchronous bursts of carbonmonoxide release," Nature Communications, Nature, vol. 13(1), pages 1-10, December.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-28997-z
    DOI: 10.1038/s41467-022-28997-z
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    1. Ph. Wernet & K. Kunnus & I. Josefsson & I. Rajkovic & W. Quevedo & M. Beye & S. Schreck & S. Grübel & M. Scholz & D. Nordlund & W. Zhang & R. W. Hartsock & W. F. Schlotter & J. J. Turner & B. Kennedy , 2015. "Orbital-specific mapping of the ligand exchange dynamics of Fe(CO)5 in solution," Nature, Nature, vol. 520(7545), pages 78-81, April.
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