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Catalytic Reduction of N2 to NH3 by an Fe–N2 Complex Featuring a C-Atom Anchor

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    Catalytic Reduction of N2 to NH3 by an Fe–N2 Complex Featuring a C-Atom Anchor
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    Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States
    [email protected]
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2014, 136, 3, 1105–1115
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    https://doi.org/10.1021/ja4114962
    Published December 18, 2013
    Copyright © 2013 American Chemical Society
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    Abstract

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    While recent spectroscopic studies have established the presence of an interstitial carbon atom at the center of the iron–molybdenum cofactor (FeMoco) of MoFe-nitrogenase, its role is unknown. We have pursued Fe–N2 model chemistry to explore a hypothesis whereby this C-atom (previously denoted as a light X-atom) may provide a flexible trans interaction with an Fe center to expose an Fe–N2 binding site. In this context, we now report on Fe complexes of a new tris(phosphino)alkyl (CPiPr3) ligand featuring an axial carbon donor. It is established that the iron center in this scaffold binds dinitrogen trans to the Calkyl-atom anchor in three distinct and structurally characterized oxidation states. Fe–Calkyl lengthening is observed upon reduction, reflective of significant ionic character in the Fe–Calkyl interaction. The anionic (CPiPr3)FeN2– species can be functionalized by a silyl electrophile to generate (CPiPr3)Fe–N2SiR3. (CPiPr3)FeN2– also functions as a modest catalyst for the reduction of N2 to NH3 when supplied with electrons and protons at −78 °C under 1 atm N2 (4.6 equiv NH3/Fe).

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    Spectroscopic data for new compounds, further experimental and computational details, and additional data on catalytic runs. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Cite this: J. Am. Chem. Soc. 2014, 136, 3, 1105–1115
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