Probing the Primary Photochemical Processes of Octahedral Iron(V) Formation with Femtosecond Mid-infrared Spectroscopy.

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 N-N bond rupture on the ground-state surface.