N_2-to-NH_3 Conversion by a triphos-Iron Catalyst and Enhanced Turnover under Photolysis
Abstract
Bridging iron hydrides are proposed to form at the active site of MoFe-nitrogenase during catalytic dinitrogen reduction to ammonia and may be key in the binding and activation of N_2 via reductive elimination of H_2. This possibility inspires the investigation of well-defined molecular iron hydrides as precursors for catalytic N_2-to-NH_3 conversion. Herein, we describe the synthesis and characterization of new P_2^(P′Ph)Fe(N_2)(H)_x systems that are active for catalytic N_2-to-NH_3 conversion. Most interestingly, we show that the yields of ammonia can be significantly increased if the catalysis is performed in the presence of mercury lamp irradiation. Evidence is provided to suggest that photo-elimination of H_2 is one means by which the enhanced activity may arise.
Additional Information
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Manuscript received: March 29, 2017; Version of record online: May 10, 2017. This work was supported by the NIH (GM070757 and a Ruth L. Kirschstein NRSA Predoctoral Fellowship to Promote Diversity in Health-Related Research to T.M.B.), and the NSF via its MRI program (NSF-1531940). We thank Lawrence Henling and Michael Takase for assistance with XRD studies, Javier Fajardo, Jr., Matthew Chalkley, and Niklas Thompson for insightful discussions, and Dr. Shabnam Hematian for assistance with GC experiments. The authors declare no conflict of interest.Attached Files
Supplemental Material - anie201703244-sup-0001-misc_information.pdf
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Additional details
- PMCID
- PMC5595421
- Eprint ID
- 77446
- Resolver ID
- CaltechAUTHORS:20170515-102546782
- NIH
- GM070757
- NIH Predoctoral Fellowship
- NSF
- CHE-1531940
- Created
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2017-05-15Created from EPrint's datestamp field
- Updated
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2021-11-15Created from EPrint's last_modified field