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Catalytic Nitrogen-to-Ammonia Conversion by Osmium and Ruthenium Complexes

Fajardo, Javier, Jr. and Peters, Jonas C. (2017) Catalytic Nitrogen-to-Ammonia Conversion by Osmium and Ruthenium Complexes. Journal of the American Chemical Society, 139 (45). pp. 16105-16108. ISSN 0002-7863.

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Despite the critical role Ru and Os complexes have played in the development of transition metal dinitrogen chemistry, they have not been shown to mediate catalytic N_2-to-NH_3 conversion (N_2RR), nor have M-N_xH_y complexes been derived from protonation of their M-N_2 precursors. To help delineate factors for N_2RR catalysis, we report on isostructural tris(phosphino)silyl Ru and Os complexes that mediate catalytic N_2RR, and compare their activities with an isostructural Fe complex. The Os system is most active, and liberates more than 120 equiv NH_3 per Os center in a single batch experiment using Cp*_2Co and [H_2NPh_2][OTf] as reductant and acid source. Isostructural Ru and Fe complexes generate little NH_3 under the same conditions. Protonation of Os-N_2– affords a structurally characterized Os=NNH_2+ hydrazido species that mediates NH_3 generation, suggesting it is a plausible intermediate of the catalysis. Inactive Os hydrides are characterized that form during catalysis.

Item Type:Article
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URLURL TypeDescription Information
Peters, Jonas C.0000-0002-6610-4414
Additional Information:© 2017 American Chemical Society. Received: September 27, 2017; Published: October 26, 2017. This work was supported by the NIH (GM070757) and the Gordon and Betty Moore Foundation. We thank Dr. Michael K. Takase and Larry Henling for crystallographic assistance. J.F.J. acknowledges support of the NSF for a Graduate Fellowship (GRFP). The authors declare no competing financial interest.
Funding AgencyGrant Number
Gordon and Betty Moore FoundationUNSPECIFIED
NSF Graduate Research FellowshipUNSPECIFIED
Issue or Number:45
Record Number:CaltechAUTHORS:20171027-140025548
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Official Citation:Catalytic Nitrogen-to-Ammonia Conversion by Osmium and Ruthenium Complexes. Javier Fajardo, Jr. and Jonas C. Peters. Journal of the American Chemical Society 2017 139 (45), 16105-16108. DOI: 10.1021/jacs.7b10204
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:82740
Deposited By: Tony Diaz
Deposited On:27 Oct 2017 21:13
Last Modified:03 Oct 2019 18:58

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