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Probing Hydrogen Bonding Interactions to Iron‐Oxido/Hydroxido Units by 57 Fe Nuclear Resonance Vibrational Spectroscopy
Author(s) -
Weitz Andrew C.,
Hill Ethan A.,
Oswald Victoria F.,
Bominaar Emile L.,
Borovik Andrew S.,
Hendrich Michael P.,
Guo Yisong
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201810227
Subject(s) - coordination sphere , chemistry , intramolecular force , trigonal bipyramidal molecular geometry , hydrogen bond , crystallography , resonance (particle physics) , molecule , stereochemistry , crystal structure , organic chemistry , atomic physics , physics
Hydrogen bonds (H‐bonds) have been shown to modulate the chemical reactivities of iron centers in iron‐containing dioxygen‐activating enzymes and model complexes. However, few examples are available that investigate how systematic changes in intramolecular H‐bonds within the secondary coordination sphere influence specific properties of iron intermediates, such as iron‐oxido/hydroxido species. Here, we used 57 Fe nuclear resonance vibrational spectroscopy (NRVS) to probe the Fe‐O/OH vibrations in a series of Fe III ‐hydroxido and Fe IV/III ‐oxido complexes with varying H‐bonding networks but having similar trigonal bipyramidal primary coordination spheres. The data show that even subtle changes in the H‐bonds to the Fe‐O/OH units result in significant changes in their vibrational frequencies, thus demonstrating the utility of NRVS in studying the effect of the secondary coordination sphere to the reactivities of iron complexes.