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High‐Frequency Fe–H Vibrations in a Bridging Hydride Complex Characterized by NRVS and DFT |
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| Authors: | Dr Vladimir Pelmenschikov Dr Leland B Gee Dr Hongxin Wang Dr K Cory MacLeod Sean F McWilliams Dr Kazimer L Skubi Prof?Dr Stephen P Cramer Prof?Dr Patrick L Holland |
| Institution: | 1. Institut für Chemie, TU Berlin, Berlin, Germany;2. Department of Chemistry, University of California, Davis, CA, USA;3. Current Address: Department of Chemistry, Stanford University, Stanford, CA, USA;4. Department of Chemistry, Yale University, New Haven, CT, USA |
| Abstract: | 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 57Fe nuclear resonance vibrational spectroscopy (NRVS) study on an Fe(μ‐H)2Fe 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. |
| Keywords: | density functional theory iron hydrides nitrogenases nuclear resonance vibrational spectroscopy |