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Probing the Primary Photochemical Processes of Octahedral Iron(V) Formation with Femtosecond Mid-infrared Spectroscopy
Ist Teil von
Chemphyschem, 2015-08, Vol.16 (11), p.2289-2293
Ort / Verlag
Weinheim: WILEY-VCH Verlag
Erscheinungsjahr
2015
Link zum Volltext
Quelle
Wiley Online Library Journals Frontfile Complete
Beschreibungen/Notizen
Species containing iron at an oxidation state higher than +III are often termed “high‐valent iron” and are considered to be key catalytic intermediates in biochemistry. Here, we report the direct time‐domain probing of the photochemical formation of an octahedral nitrido iron(V) complex through dinitrogen cleavage from an diazido iron(III) precursor by using femtosecond mid‐infrared (MIR) spectroscopy. From the time‐resolved vibrational spectra, a mechanism is suggested for the photooxidation of the metal within 10 ps. This mechanism involves an initial ultrafast non‐adiabatic transition, followed by a quasithermal NN bond rupture on the ground‐state surface.
Right on time: Femtosecond UV‐pump mid‐infrared‐probe spectroscopy was used to track the primary events leading to the generation of a four‐fold symmetrical nitrido iron(V) complex from an azido iron(III) precursor in solution.