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Probing the Primary Photochemical Processes of Octahedral Iron(V) Formation with Femtosecond Mid‐infrared Spectroscopy
Author(s) -
TorresAlacan Joel,
Lindner Jörg,
Vöhringer Peter
Publication year - 2015
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201500370
Subject(s) - femtosecond , femtochemistry , photochemistry , infrared , spectroscopy , infrared spectroscopy , octahedron , chemistry , materials science , crystallography , laser , optics , crystal structure , organic chemistry , physics , quantum mechanics
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.