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Cover Picture: Probing the Primary Photochemical Processes of Octahedral Iron(V) Formation with Femtosecond Mid‐infrared Spectroscopy (ChemPhysChem 11/2015)
Author(s) -
TorresAlacan Joel,
Lindner Jörg,
Vöhringer Peter
Publication year - 2015
Publication title -
chemphyschem
Language(s) - English
Resource type - Reports
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201590057
Subject(s) - photochemistry , chemistry , femtosecond , spectroscopy , ground state , infrared spectroscopy , femtochemistry , ultrafast laser spectroscopy , photodissociation , oxidation state , infrared , absorption spectroscopy , catalysis , laser , biochemistry , physics , organic chemistry , quantum mechanics , optics
Compounds containing iron at an oxidation state higher than +III are commonly termed “high‐valent iron”. Such species play a prominent catalytic role in many enzymatic reactions. On p 2289, P. Vöhringer et al. describe the generation of a high‐valent nitrido–iron(V) species from a ferric azide precursor complex in solution under ambient conditions with femtosecond ultraviolet laser pulses. The primary processes involved in high‐valent iron formation are studied using ultrafast time‐resolved mid‐infrared spectroscopy. The mechanism that leads to dinitrogen cleavage with oxidation of the metal center from +III to +V, following absorption of an incident UV photon, involves a primary nonadiabatic transition back to the electronic ground state and a subsequent quasithermal barrier crossing along the intraligand NN bond.