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Electrophile-promoted Fe-to-N₂ hydride migration in highly reduced Fe(N₂)(H) complexes

Deegan, Meaghan M. and Peters, Jonas C. (2018) Electrophile-promoted Fe-to-N₂ hydride migration in highly reduced Fe(N₂)(H) complexes. Chemical Science, 9 (29). pp. 6264-6270. ISSN 2041-6520. PMCID PMC6063139. doi:10.1039/C8SC02380H.

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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 N₂-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=NNR₂) derived from N₂ 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
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URLURL TypeDescription CentralArticle
Deegan, Meaghan M.0000-0002-7633-2074
Peters, Jonas C.0000-0002-6610-4414
Alternate Title:Electrophile-promoted Fe-to-N2 hydride migration in highly reduced Fe(N2)(H) complexes, Electrophile-promoted Fe-to-N_2 hydride migration in highly reduced Fe(N_2)(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.
Funding AgencyGrant Number
NIHGM 070757
Royal Society of ChemistryUNSPECIFIED
Issue or Number:29
PubMed Central ID:PMC6063139
Record Number:CaltechAUTHORS:20180705-154047668
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:87573
Deposited By: George Porter
Deposited On:06 Jul 2018 15:04
Last Modified:09 Mar 2022 18:56

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