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Nitrogen Fixation via a Terminal Fe(IV) Nitride

Thompson, Niklas B. and Green, Michael T. and Peters, Jonas C. (2017) Nitrogen Fixation via a Terminal Fe(IV) Nitride. Journal of the American Chemical Society, 139 (43). pp. 15312-15315. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20171010-095936880

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Abstract

Terminal iron nitrides (Fe≡N) have been proposed as intermediates of (bio)catalytic nitrogen fixation, yet experimental evidence to support this hypothesis has been lacking. In particular, no prior synthetic examples of terminal Fe≡N species have been derived from N_2. Here we show that a nitrogen-fixing Fe–N_2 catalyst can be protonated to form a neutral Fe(NNH_2) hydrazido(2−) intermediate, which, upon further protonation, heterolytically cleaves the N–N bond to release [Fe^(IV)≡N]^+ and NH_3. These observations provide direct evidence for the viability of a Chatt-type (distal) mechanism for Fe-mediated N_2-to-NH_3 conversion. The physical oxidation state range of the Fe complexes in this transformation is buffered by covalency with the ligand, a feature of possible relevance to catalyst design in synthetic and natural systems that facilitate multiproton/multielectron redox processes.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.7b09364DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jacs.7b09364PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jacs.7b09364PublisherSupporting Information
ORCID:
AuthorORCID
Thompson, Niklas B.0000-0003-2745-4945
Peters, Jonas C.0000-0002-6610-4414
Additional Information:© 2017 American Chemical Society. Received: September 1, 2017; Published: October 9, 2017. We thank M. Latimer, E. Nelson, C. Krest, C. Miller, and K. Mittra for assistance with synchrotron measurements. This work was supported by the Resnick Sustainability Institute at Caltech (Graduate Fellowship, N.B.T.), as well as the NIH (GM 070757). Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. Additional notes in the Supporting Information. The authors declare no competing financial interest.
Group:Resnick Sustainability Institute
Funders:
Funding AgencyGrant Number
Resnick Sustainability InstituteUNSPECIFIED
NIHGM-070757
Department of Energy (DOE)DE-AC02-76SF00515
Record Number:CaltechAUTHORS:20171010-095936880
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20171010-095936880
Official Citation:Nitrogen Fixation via a Terminal Fe(IV) Nitride. Niklas B. Thompson, Michael T. Green, and Jonas C. Peters. Journal of the American Chemical Society 2017 139 (43), 15312-15315. DOI: 10.1021/jacs.7b09364
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:82248
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:10 Oct 2017 17:25
Last Modified:27 Nov 2017 18:36

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