Photodissociation of ironpentacarbonyl acts as a carbonmonoxide geyser

2022-03-14

Transition metal complexes are efficiently acting as catalysts and are used for energy conversion in photochemical processes because of easily accessible close-lying electronic states. Computer simulations are essential to resolve mechanistic details determining the reaction pathway.

In theoretical simulation, we have followed the non-adiabatic dynamics in the photodissociation of ironpentacarbonyl, in the sub-picosecond regime, which is challenging to access experimentally.

We can resolve the initial events and find that the bright metal-to-ligand charge-transfer transition induces synchronous Fe-C oscillations, followed by transitions for dissociative metal-centered excited states. This leads to periodically reoccurring release of carbonmonoxide and creation of a catalytically active irontetracarbonyl fragment.

Significance for photocatalysis

The work was lead by Ambar Banerjee and Michael Odelius at Fysikum, Stockholm University.

“This detailed mechanistic insight will have to be explored experimentally, and might be an essential ingredient in understanding the photophysics and photochemistry of transition metal carbonyls and give a handle on improved design of photocatalysts”, says the lead author Ambar Banerjee.

Article Reference

Banerjee, A., Coates, M.R., Kowalewski, M. et al. Photoinduced bond oscillations in ironpentacarbonyl give delayed synchronous bursts of carbonmonoxide release. Nat Commun 13, 1337 (2022). https://doi.org/10.1038/s41467-022-28997-z

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Philippe Wernet

Last modified: 2022-02-22