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Electrophile-promoted Fe-to-N_2 hydride migration in highly reduced Fe(N_2)(H) complexes

Deegan, Meaghan M. and Peters, Jonas C. (2018) Electrophile-promoted Fe-to-N_2 hydride migration in highly reduced Fe(N_2)(H) complexes. Chemical Science, 9 (29). pp. 6264-6270. ISSN 2041-6520 . PMCID PMC6063139. http://resolver.caltech.edu/CaltechAUTHORS:20180705-154047668

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Abstract

One of the emerging challenges associated with developing robust synthetic nitrogen fixation catalysts is the competitive formation of hydride species that can play a role in catalyst deactivation or lead to undesired hydrogen evolution reactivity (HER). It is hence desirable to devise synthetic systems where metal hydrides can migrate directly to coordinated N2 in reductive N–H bond-forming steps, thereby enabling productive incorporation into desired reduced N_2-products. Relevant examples of this type of reactivity in synthetic model systems are limited. In this manuscript we describe the migration of an iron hydride (Fe-H) to N_α of a disilylhydrazido(2-) ligand (Fe=NNR_2) derived from N_2 via double-silylation in a preceding step. This is an uncommon reactivity pattern in general; well-characterized examples of hydride/alkyl migrations to metal heteroatom bonds (e.g., (R)M=NR′ → M–N(R)R′) are very rare. Mechanistic data establish the Fe-to-N_α hydride migration to be intramolecular. The resulting disilylhydrazido(1-) intermediate can be isolated by trapping with CN^tBu, and the disilylhydrazine product can then be liberated upon treatment with an additional acid equivalent, demonstrating the net incorporation of an Fe-H equivalent into an N-fixed product.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1039/C8SC02380HDOIArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6063139PubMed CentralArticle
ORCID:
AuthorORCID
Peters, Jonas C.0000-0002-6610-4414
Alternate Title:Electrophile-promoted Fe-to-N2 hydride migration in highly reduced Fe(N2)(H) complexes
Additional Information:© 2018 the Author(s). This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. All publication charges for this article have been paid for by the Royal Society of Chemistry. Received 31st May 2018, Accepted 26th June 2018. First published on 29th June 2018. This work was supported by the NIH (GM 070757). The authors are grateful to Larry Henling and Mike Takase for crystallographic assistance. We thank Trixia Buscagan for preliminary data on complex 4. Conflicts of interest: There are no conflicts to declare.
Funders:
Funding AgencyGrant Number
NIHGM 070757
PubMed Central ID:PMC6063139
Record Number:CaltechAUTHORS:20180705-154047668
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20180705-154047668
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:87573
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:06 Jul 2018 15:04
Last Modified:20 Aug 2018 14:38

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