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High‐Frequency Fe–H Vibrations in a Bridging Hydride Complex Characterized by NRVS and DFT
Author(s) -
Pelmenschikov Vladimir,
Gee Leland B.,
Wang Hongxin,
MacLeod K. Cory,
McWilliams Sean F.,
Skubi Kazimer L.,
Cramer Stephen P.,
Holland Patrick L.
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201804601
Subject(s) - hydride , density functional theory , bridging (networking) , infrared spectroscopy , chemistry , molecular vibration , crystallography , infrared , materials science , hydrogen , molecule , computational chemistry , physics , computer network , organic chemistry , computer science , optics
High‐spin iron species with bridging hydrides have been detected in species trapped during nitrogenase catalysis, but there are few general methods of evaluating Fe−H bonds in high‐spin multinuclear iron systems. An 57 Fe nuclear resonance vibrational spectroscopy (NRVS) study on an Fe(μ‐H) 2 Fe model complex reveals Fe−H stretching vibrations for bridging hydrides at frequencies greater than 1200 cm −1 . These isotope‐sensitive vibrational bands are not evident in infrared (IR) spectra, showing the power of NRVS for identifying hydrides in this high‐spin iron system. Complementary density functional theory (DFT) calculations elucidate the normal modes of the rhomboidal iron hydride core.