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  In search of metal hydrides: an X-ray absorption and emission study of [NiFe] hydrogenase model complexes

Hugenbruch, S., Shafaat, H. S., Krämer, T., Delgado-Jaime, M. U., Weber, K., Neese, F., et al. (2016). In search of metal hydrides: an X-ray absorption and emission study of [NiFe] hydrogenase model complexes. Physical Chemistry Chemical Physics, 18(16), 10688-10699. doi:10.1039/C5CP07293J.

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Hugenbruch, Stefan1, Author           
Shafaat, Hannah S.2, 3, Author           
Krämer, Tobias1, 4, Author           
Delgado-Jaime, Mario Ulises1, 5, Author           
Weber, Katharina2, Author           
Neese, Frank1, Author           
Lubitz, Wolfgang2, Author           
DeBeer, Serena1, 6, Author           
1Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              
2Research Department Lubitz, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023873              
3The Ohio State University, Department of Chemistry and Biochemistry, 100 West 18th Avenue, Columbus, OH 43210-1173, USA, ou_persistent22              
4Heriot-Watt University, Institute of Chemical Sciences, Edinburgh EH14 4AS, UK , ou_persistent22              
5Inorganic Chemistry and Catalysis Group, Debye Institute for Nanomaterials Science, Utrecht University , Universiteitsweg 99, Utrecht 3584 CG, The Netherlands, ou_persistent22              
6Cornell University, Department of Chemistry and Chemical Biology, Ithaca, New York, USA , ou_persistent22              


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 Abstract: Metal hydrides are invoked as important intermediates in both chemical and biological H2 production. In the [NiFe] hydrogenase enzymes, pulsed EPR and high-resolution crystallography have argued that the hydride interacts primarily at the Ni site. In contrast, in [NiFe] hydrogenase model complexes, it is observed that the bridging hydride interacts primarily with the Fe. Herein, we utilize a combination of Ni and Fe X-ray absorption (XAS) and emission (XES) spectroscopies to examine the contribution of the bridging hydride to the observed spectral features in [(dppe)Ni(μ-pdt)(μ-H)Fe(CO)3]+. The corresponding data on (dppe)Ni(μ-pdt)Fe(CO)3 are used as a reference for the changes that occur in the absence of a hydride bridge. For further interpretation of the observed spectral features, all experimental spectra were calculated using a density functional theory (DFT) approach, with excellent agreement between theory and experiment. It is found that the iron valence-to-core (VtC) XES spectra reveal clear signatures for the presence of a Fe–H interaction in the hydride bridged model complex. In contrast, the Ni VtC XES spectrum largely reflects changes in the local Ni geometry and shows little contribution from a Ni–H interaction. A stepwise theoretical analysis of the hydride contribution and the Ni site symmetry provides insights into the factors, which govern the different metal–hydride interactions in both the model complexes and the enzyme. Furthermore, these results establish the utility of two-color XES to reveal important insights into the electronic structure of various metal–hydride species.


Language(s): eng - English
 Dates: 2015-11-262016-02-152016-04-28
 Publication Status: Published in print
 Pages: 12
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/C5CP07293J
 Degree: -



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Title: Physical Chemistry Chemical Physics
  Abbreviation : Phys. Chem. Chem. Phys.
Source Genre: Journal
Publ. Info: Cambridge, England : Royal Society of Chemistry
Pages: - Volume / Issue: 18 (16) Sequence Number: - Start / End Page: 10688 - 10699 Identifier: ISSN: 1463-9076
CoNE: https://pure.mpg.de/cone/journals/resource/954925272413_1