IDEAS home Printed from https://ideas.repec.org/a/nat/natcom/v6y2015i1d10.1038_ncomms6865.html
   My bibliography  Save this article

Evidence for an oxygen evolving iron–oxo–cerium intermediate in iron-catalysed water oxidation

Author

Listed:
  • Zoel Codolà

    (Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus de Montilivi)

  • Laura Gómez

    (University of Minnesota)

  • Scott T. Kleespies

    (Serveis Tècnics de Recerca (STR), Parc Cientific i Tecnològic, Universitat de Girona)

  • Lawrence Que Jr

    (Serveis Tècnics de Recerca (STR), Parc Cientific i Tecnològic, Universitat de Girona)

  • Miquel Costas

    (Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus de Montilivi)

  • Julio Lloret-Fillol

    (Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus de Montilivi)

Abstract

The non-haem iron complex α-[FeII(CF3SO3)2(mcp)] (mcp=(N,N′-dimethyl-N,N′-bis(2-pyridylmethyl)-1,2-cis-diaminocyclohexane) reacts with CeIV to oxidize water to O2, representing an iron-based functional model for the oxygen evolving complex of photosystem II. Here we trap an intermediate, characterized by cryospray ionization high resolution mass spectrometry and resonance Raman spectroscopy, and formulated as [(mcp)FeIV(O)(μ-O)CeIV(NO3)3]+, the first example of a well-characterized inner-sphere complex to be formed in cerium(IV)-mediated water oxidation. The identification of this reactive FeIV–O–CeIV adduct may open new pathways to validate mechanistic notions of an analogous MnV–O–CaII unit in the oxygen evolving complex that is responsible for carrying out the key O–O bond forming step.

Suggested Citation

  • Zoel Codolà & Laura Gómez & Scott T. Kleespies & Lawrence Que Jr & Miquel Costas & Julio Lloret-Fillol, 2015. "Evidence for an oxygen evolving iron–oxo–cerium intermediate in iron-catalysed water oxidation," Nature Communications, Nature, vol. 6(1), pages 1-10, May.
    • Handle: RePEc:nat:natcom:v:6:y:2015:i:1:d:10.1038_ncomms6865
    DOI: 10.1038/ncomms6865
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/ncomms6865
    File Function: Abstract
    Download Restriction: no
    File URL: https://libkey.io/10.1038/ncomms6865?utm_source=ideas
    LibKey link: if access is restricted and if your library uses this service, LibKey will redirect you to where you can use your library subscription to access this item
    ---><---

    More about this item

    Statistics

    Access and download statistics

    Corrections

    All material on this site has been provided by the respective publishers and authors. You can help correct errors and omissions. When requesting a correction, please mention this item's handle: RePEc:nat:natcom:v:6:y:2015:i:1:d:10.1038_ncomms6865. See general information about how to correct material in RePEc.

    If you have authored this item and are not yet registered with RePEc, we encourage you to do it here. This allows to link your profile to this item. It also allows you to accept potential citations to this item that we are uncertain about.

    We have no bibliographic references for this item. You can help adding them by using this form .

    If you know of missing items citing this one, you can help us creating those links by adding the relevant references in the same way as above, for each refering item. If you are a registered author of this item, you may also want to check the "citations" tab in your RePEc Author Service profile, as there may be some citations waiting for confirmation.

    For technical questions regarding this item, or to correct its authors, title, abstract, bibliographic or download information, contact: Sonal Shukla or Springer Nature Abstracting and Indexing (email available below). General contact details of provider: http://www.nature.com .

    Please note that corrections may take a couple of weeks to filter through the various RePEc services.

    IDEAS is a RePEc service. RePEc uses bibliographic data supplied by the respective publishers.