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Hydride bridge in [NiFe]-hydrogenase observed by nuclear resonance vibrational spectroscopy

Journal Article · · Nature Communications
DOI:https://doi.org/10.1038/ncomms8890· OSTI ID:1256036
 [1];  [1];  [2];  [3];  [4];  [1];  [1];  [3];  [5];  [5];  [6];  [7];  [1];  [2]
  1. Max Planck Inst. for Chemical Energy Conversion, Mulheim, (Germany)
  2. Univ. of California, Davis, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Univ. of Illinois, Urbana, IL (United States)
  4. Technical Univ. Berlin (Germany)
  5. Univ. of California, Davis, CA (United States)
  6. SPring-8/JASRI, Hyogo (Japan)
  7. RIKEN SPring-8, Hyogo (Japan)
+ Show Author Affiliations
The metabolism of many anaerobes relies on [NiFe]-hydrogenases, whose characterization when bound to substrates has proven non-trivial. Presented here is direct evidence for a hydride bridge in the active site of the 57Fe-labelled fully reduced Ni-R form of Desulfovibrio vulgaris Miyazaki F [NiFe]-hydrogenase. A unique ‘wagging’ mode involving H- motion perpendicular to the Ni(μ-H)57Fe plane was studied using 57Fe-specific nuclear resonance vibrational spectroscopy and density functional theory (DFT) calculations. On Ni(μ-D)57Fe deuteride substitution, this wagging causes a characteristic perturbation of Fe–CO/CN bands. Spectra have been interpreted by comparison with Ni(μ-H/D)57Fe enzyme mimics [(dppe)Ni(μ-pdt)(μ-H/D)57Fe(CO)3]+ and DFT calculations, which collectively indicate a low-spin Ni(II)(μ-H)Fe(II) core for Ni-R, with H- binding Ni more tightly than Fe. Lastly, the present methodology is also relevant to characterizing Fe–H moieties in other important natural and synthetic catalysts.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
Grant/Contract Number:
FG02-90ER14146
OSTI ID:
1256036
Journal Information:
Nature Communications, Journal Name: Nature Communications Vol. 6; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (12)

Nitrosylation of Nitric-Oxide-Sensing Regulatory Proteins Containing [4Fe-4S] Clusters Gives Rise to Multiple Iron-Nitrosyl Complexes journal October 2016
What Can Be Learned from Nuclear Resonance Vibrational Spectroscopy: Vibrational Dynamics and Hemes journal September 2017
QM/MM Investigation of the Role of a Second Coordination Shell Arginine in [NiFe]-Hydrogenases journal May 2018
Edwardsiella tarda Sip2: A Serum-Induced Protein That Is Essential to Serum Survival, Acid Resistance, Intracellular Replication, and Host Infection journal May 2018
Computational Insights into the Reaction Mechanisms of Nickel-Catalyzed Hydrofunctionalizations and Nickel-Dependent Enzymes journal March 2018
High-Frequency Fe-H Vibrations in a Bridging Hydride Complex Characterized by NRVS and DFT journal June 2018
Nitrosylation of Nitric-Oxide-Sensing Regulatory Proteins Containing [4Fe-4S] Clusters Gives Rise to Multiple Iron-Nitrosyl Complexes journal October 2016
High-Frequency Fe-H Vibrations in a Bridging Hydride Complex Characterized by NRVS and DFT journal June 2018
Mechanism of hydrogen activation by [NiFe] hydrogenases journal November 2015
Vibrational dynamics (IR, Raman, NRVS) and a DFT study of a new antitumor tetranuclearstannoxane cluster, Sn( iv )-oxo-{di-o-vanillin} dimethyl dichloride journal January 2016
Comprehensive reaction mechanisms at and near the Ni–Fe active sites of [NiFe] hydrogenases journal January 2018
Coumarin centered copper( ii ) complex with appended-imidazole as cancer chemotherapeutic agents against lung cancer: molecular insight via DFT-based vibrational analysis journal January 2017

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY