Synthesis and Reactivity of Iron Acyl Complexes Modeling the Active Site of [Fe]-Hydrogenase

Dafa Chen, Rosario Scopelliti and Xile Hu*
Laboratory of Inorganic Synthesis and Catalysis, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne (EPFL), SB-ISIC-LSCI, BCH 3305, Lausanne 1015, Switzerland
J. Am. Chem. Soc., 2010, 132 (3), pp 928–929
DOI: 10.1021/ja9100485
Publication Date (Web): December 30, 2009
Copyright © 2009 American Chemical Society

Abstract

Abstract Image

A [FeIIFeII] dithiolate complex containing acyl and carbonyl ligands was synthesized. The diiron complex reacted with phosphine, cyanide, isocyanide, and CO to give monomeric FeII complexes reproducing the first coordination sphere of the active site of [Fe]-hydrogenase (H2-forming methylene-tetrahydromethanopterin dehydrogenase, Hmd) in various states. All the acyl and carbonyl carbons in the diiron complex underwent facile isotopic exchange with 13CO via monomeric Fe tricarbonyl intermediates.

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This article has been cited by 5 ACS Journal articles (5 most recent appear below).

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    Synthesis and Characterization of a Series of Model Complexes of the Active Site of [Fe]-Hydrogenase (Hmd)

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    Inorganic Chemistry2011 Article ASAP
    • Synthesis and Characterization of a Series of Model Complexes of the Active Site of [Fe]-Hydrogenase (Hmd)

      Dafa Chen, Annegret Ahrens-Botzong, Volker Schünemann, Rosario Scopelliti, and Xile Hu
      Inorganic Chemistry2011 Article ASAP

      A series of Fe complexes were synthesized and characterized as small molecule mimics for the active site of [Fe]-hydrogenase (Hmd). The collection includes both structurally new compounds and analogues of previously reported models. These complexes ...

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    Rearrangement of the Tris(2-pyridylthio)methanido Ligand in an Iron(II) Complex Containing an Fe−C Bond

    Partha Halder and Tapan Kanti Paine
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    • Rearrangement of the Tris(2-pyridylthio)methanido Ligand in an Iron(II) Complex Containing an Fe−C Bond

      Partha Halder and Tapan Kanti Paine
      Inorganic Chemistry2011 50 (3), 708-710

      Iron(II) tris(2-pyridylthio)methanido (1) containing an Fe−C bond, obtained from the reaction of tris(2-pyridylthio)methane (HL1) and iron(II) triflate, reacts with protic acid to generate iron(II) bis(2-pyridylthio)carbene (1a). The carbene complex is ...

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    The Third Hydrogenase: More Natural Organometallics

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    Organometallics2010 29 (23), 6146-6156
    • The Third Hydrogenase: More Natural Organometallics

      Joseph A. Wright, Peter J. Turrell, and Christopher J. Pickett
      Organometallics2010 29 (23), 6146-6156

      The [Fe]-hydrogenase, also known as “H2-forming methylenetetrahydromethanopterin dehydrogenase” (Hmd) or “iron−sulfur cluster-free hydrogenase”, is the third distinct class of hydrogenase enzyme to be discovered. In the presence of its carbocation ...

  • Cover Image

    Iron Acyl Thiolato Carbonyls: Structural Models for the Active Site of the [Fe]-Hydrogenase (Hmd)

    Aaron M. Royer, Marco Salomone-Stagni, Thomas B. Rauchfuss, and Wolfram Meyer-Klaucke
    Journal of the American Chemical Society2010 132 (47), 16997-17003
    • Iron Acyl Thiolato Carbonyls: Structural Models for the Active Site of the [Fe]-Hydrogenase (Hmd)

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      Journal of the American Chemical Society2010 132 (47), 16997-17003

      Phosphine-modified thioester derivatives are shown to serve as efficient precursors to phosphine-stabilized ferrous acyl thiolato carbonyls, which replicate key structural features of the active site of the hydrogenase Hmd. The reaction of Ph2PC6H4C(O)SPh ...

  • Cover Image

    Perspectives on How Nature Employs the Principles of Organometallic Chemistry in Dihydrogen Activation in Hydrogenases

    John C. Gordon and Gregory J. Kubas
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    • Perspectives on How Nature Employs the Principles of Organometallic Chemistry in Dihydrogen Activation in Hydrogenases

      John C. Gordon and Gregory J. Kubas
      Organometallics2010 29 (21), 4682-4701

      Relatively recent developments in metalloenzyme and organometallic chemistry have targeted a growing link between these outwardly incongruous fields, giving birth to a merger now popularly termed “bio-organometallic” chemistry. The astonishing discovery ...

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History

  • Published In Issue January 27, 2010
  • Article ASAPDecember 30, 2009
  • Received: November 27, 2009

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