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Catalytic Reduction of N_2 to NH_3 by an Fe−N_2 Complex Featuring a C‑Atom Anchor

Creutz, Sidney E. and Peters, Jonas C. (2014) Catalytic Reduction of N_2 to NH_3 by an Fe−N_2 Complex Featuring a C‑Atom Anchor. Journal of the American Chemical Society, 136 (3). pp. 1105-1115. ISSN 0002-7863. PMCID PMC3933546. http://resolver.caltech.edu/CaltechAUTHORS:20140113-132603289

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Abstract

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–N_2 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–N_2 binding site. In this context, we now report on Fe complexes of a new tris(phosphino)alkyl (CP^(iPr)_3) ligand featuring an axial carbon donor. It is established that the iron center in this scaffold binds dinitrogen trans to the C_(alkyl)-atom anchor in three distinct and structurally characterized oxidation states. Fe–C_(alkyl) lengthening is observed upon reduction, reflective of significant ionic character in the Fe–C_(alkyl) interaction. The anionic (CP^(iPr)_3)FeN_2^– species can be functionalized by a silyl electrophile to generate (CP^(iPr)_3)Fe–N_2SiR_3. (CP^(iPr)_3)FeN_2^– also functions as a modest catalyst for the reduction of N_2 to NH_3 when supplied with electrons and protons at −78 °C under 1 atm N_2 (4.6 equiv NH_3/Fe).


Item Type:Article
Related URLs:
URLURL TypeDescription
http://pubs.acs.org/doi/abs/10.1021/ja4114962PublisherArticle
http://dx.doi.org/10.1021/ja4114962DOIArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3933546/PubMed CentralArticle
Additional Information:© 2013 American Chemical Society. Published In Issue January 22, 2014; Article ASAP January 09, 2014; Just Accepted ManuscriptDecember 18, 2013; Received: November 11, 2013. This work was supported by the NIH (GM 070757) and the Gordon and Betty Moore Foundation, and through the NSF via a GRFP award to S.E.C. Larry Henling and Dr. Tzu-Pin Lin are thanked for their assistance with X-ray crystallography. Jon Rittle is thanked for testing the catalytic activity of [C^(Si)P^(Ph)_3]-FeN_2^−.
Funders:
Funding AgencyGrant Number
NIHGM 070757
Gordon and Betty Moore FoundationUNSPECIFIED
NSF Graduate Research FellowshipUNSPECIFIED
PubMed Central ID:PMC3933546
Record Number:CaltechAUTHORS:20140113-132603289
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20140113-132603289
Official Citation:Creutz, S. E., & Peters, J. C. (2013). Catalytic Reduction of N2 to NH3 by an Fe–N2 Complex Featuring a C-Atom Anchor. Journal of the American Chemical Society, 136(3), 1105-1115. doi: 10.1021/ja4114962
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:43344
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:13 Jan 2014 21:56
Last Modified:24 Jul 2017 20:53

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