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Redox active iron nitrosyl units in proton reduction electrocatalysis

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  • Chung-Hung Hsieh

    (Texas A&M University)

  • Shengda Ding

    (Texas A&M University)

  • Özlen F. Erdem

    (Max Planck Institute for Chemical Energy Conversion)

  • Danielle J. Crouthers

    (Texas A&M University)

  • Tianbiao Liu

    (Center for Molecular Electrocatalysis, Pacific Northwest National Laboratory)

  • Charles C. L. McCrory

    (Joint Center for Artificial Photosynthesis, California Institute of Technology)

  • Wolfgang Lubitz

    (Max Planck Institute for Chemical Energy Conversion)

  • Codrina V. Popescu

    (Ursinus College)

  • Joseph H. Reibenspies

    (Texas A&M University)

  • Michael B. Hall

    (Texas A&M University)

  • Marcetta Y. Darensbourg

    (Texas A&M University)

Abstract

Base metal, molecular catalysts for the fundamental process of conversion of protons and electrons to dihydrogen, remain a substantial synthetic goal related to a sustainable energy future. Here we report a diiron complex with bridging thiolates in the butterfly shape of the 2Fe2S core of the [FeFe]-hydrogenase active site but with nitrosyl rather than carbonyl or cyanide ligands. This binuclear [(NO)Fe(N2S2)Fe(NO)2]+ complex maintains structural integrity in two redox levels; it consists of a (N2S2)Fe(NO) complex (N2S2=N,N′-bis(2-mercaptoethyl)-1,4-diazacycloheptane) that serves as redox active metallodithiolato bidentate ligand to a redox active dinitrosyl iron unit, Fe(NO)2. Experimental and theoretical methods demonstrate the accommodation of redox levels in both components of the complex, each involving electronically versatile nitrosyl ligands. An interplay of orbital mixing between the Fe(NO) and Fe(NO)2 sites and within the iron nitrosyl bonds in each moiety is revealed, accounting for the interactions that facilitate electron uptake, storage and proton reduction.

Suggested Citation

  • Chung-Hung Hsieh & Shengda Ding & Özlen F. Erdem & Danielle J. Crouthers & Tianbiao Liu & Charles C. L. McCrory & Wolfgang Lubitz & Codrina V. Popescu & Joseph H. Reibenspies & Michael B. Hall & Marce, 2014. "Redox active iron nitrosyl units in proton reduction electrocatalysis," Nature Communications, Nature, vol. 5(1), pages 1-8, May.
    • Handle: RePEc:nat:natcom:v:5:y:2014:i:1:d:10.1038_ncomms4684
    DOI: 10.1038/ncomms4684
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