Catalytic transfer hydrogenation of N₂ to NH₃ via a photoredox catalysis strategy
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1.
California Institute of Technology
Abstract
Inspired by momentum in applications of reductive photoredox catalysis to organic synthesis, photodriven transfer hydrogenations toward deep (>2 e⁻) reductions of small molecules are attractive compared to using harsh chemical reagents. Noteworthy in this context is the nitrogen reduction reaction (N₂RR), where a synthetic photocatalyst system had yet to be developed. Noting that a reduced Hantzsch ester (HEH₂) and related organic structures can behave as 2 e⁻/2 H⁺ photoreductants, we show here that, when partnered with a suitable catalyst (Mo) under blue light irradiation, HEH₂ facilitates delivery of successive H₂ equivalents for the 6 e⁻/6 H⁺ catalytic reduction of N₂ to NH₃; this catalysis is enhanced by addition of a photoredox catalyst (Ir). Reductions of additional substrates (nitrate and acetylene) are also described.
Additional Information
© 2022 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution License 4.0 (CC BY). We thank the Dow Next Generation Educator Fund and Instrumentation Grants for support of the NMR facility at Caltech. The Beckman Institute Laser Resource Center and J. R. Winkler are acknowledged for providing support with steady-state luminescence experiments. We also thank the Resnick Sustainability Institute at Caltech for enabling facilities, including its Water and Environment Laboratory (WEL). This work was supported by the National Institutes of Health (R01 GM-075757). E.A.B. acknowledges the support of the National Science Foundation for a Graduate Research Fellowship under grant no. DGE-1745301. Author contributions: Conceptualization: C.M.J. and J.C.P. Methodology: C.M.J., E.A.B., and J.C.P. Investigation: C.M.J. and E.A.B. Visualization: C.M.J., E.A.B., and J.C.P. Funding acquisition: E.A.B. and J.C.P. Project administration: J.C.P. Supervision: J.C.P. Writing—original draft: C.M.J. and E.A.B. Writing—review and editing: C.M.J., E.A.B., and J.C.P. Data and materials availability: All data needed to evaluate the conclusions in the paper are present in the paper and/or the Supplementary Materials. The authors declare that they have no competing interests.Attached Files
Published - sciadv.ade3510.pdf
Supplemental Material - sciadv.ade3510_sm.pdf
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Additional details
- Alternative title
- Catalytic transfer hydrogenation of N2 to NH3 via a photoredox catalysis strategy
- PMCID
- PMC9604530
- Eprint ID
- 118301
- Resolver ID
- CaltechAUTHORS:20221212-795726500.3
- Dow Next Generation Educator Fund
- R01 GM-075757
- NIH
- DGE-1745301
- NSF Graduate Research Fellowship
- Created
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2023-01-13Created from EPrint's datestamp field
- Updated
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2023-07-06Created from EPrint's last_modified field
- Caltech groups
- Resnick Sustainability Institute