skip to main content

DOE PAGESDOE PAGES

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

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.
Authors:
 [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)
Publication Date:
OSTI Identifier:
1256036
Grant/Contract Number:
FG02-90ER14146
Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 6; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Research Org:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY