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Catalytic N₂-to-NH₃ (or -N₂H₄) Conversion by Well-Defined Molecular Coordination Complexes

Chalkley, Matthew J. and Drover, Marcus W. and Peters, Jonas C. (2020) Catalytic N₂-to-NH₃ (or -N₂H₄) Conversion by Well-Defined Molecular Coordination Complexes. Chemical Reviews, 120 (12). pp. 5582-5636. ISSN 0009-2665. PMCID PMC7493999. doi:10.1021/acs.chemrev.9b00638.

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Nitrogen fixation, the six-electron/six-proton reduction of N₂, to give NH₃, is one of the most challenging and important chemical transformations. Notwithstanding the barriers associated with this reaction, significant progress has been made in developing molecular complexes that reduce N₂ into its bioavailable form, NH₃. This progress is driven by the dual aims of better understanding biological nitrogenases and improving upon industrial nitrogen fixation. In this review, we highlight both mechanistic understanding of nitrogen fixation that has been developed, as well as advances in yields, efficiencies, and rates that make molecular alternatives to nitrogen fixation increasingly appealing. We begin with a historical discussion of N₂ functionalization chemistry that traverses a timeline of events leading up to the discovery of the first bona fide molecular catalyst system and follow with a comprehensive overview of d-block compounds that have been targeted as catalysts up to and including 2019. We end with a summary of lessons learned from this significant research effort and last offer a discussion of key remaining challenges in the field.

Item Type:Article
Related URLs:
URLURL TypeDescription CentralArticle
Chalkley, Matthew J.0000-0002-0484-7335
Drover, Marcus W.0000-0002-2186-1040
Peters, Jonas C.0000-0002-6610-4414
Additional Information:© 2020 American Chemical Society. Received 9 October 2019. Published online 30 April 2020. This article is part of the Reactivity of Nitrogen from the Ground to the Atmosphere special issue. The authors are grateful to NIH (GM-070757) for ongoing support of their work exploring (L_n)Fe(N_xH_y) model systems of biological nitrogenases and the Department of Energy (DOE-0235032) for supporting their research towards electrocatalytic N₂RR systems. M.W.D. acknowledges NSERC (Banting PDF award to MWD), and M.W.D./M.J.C. thank the Resnick Sustainability Institute at Caltech for fellowships. Dr. Cooper Citek, Dr. Pablo G. Barros, Javier Fajardo Jr., Nina X. Gu, Dr. Heejun Lee, Dr. Alonso Rosas, and Dirk J. Schild are thanked for providing helpful discussion. Author Contributions: M.J.C. and M.W.D. contributed equally. The authors declare no competing financial interest.
Group:Resnick Sustainability Institute
Funding AgencyGrant Number
Department of Energy (DOE)DOE-0235032
Natural Sciences and Engineering Research Council of Canada (NSERC)UNSPECIFIED
Resnick Sustainability InstituteUNSPECIFIED
Issue or Number:12
PubMed Central ID:PMC7493999
Record Number:CaltechAUTHORS:20200430-151240025
Persistent URL:
Official Citation:Catalytic N2-to-NH3 (or -N2H4) Conversion by Well-Defined Molecular Coordination Complexes. Matthew J. Chalkley, Marcus W. Drover, and Jonas C. Peters. Chemical Reviews 2020 120 (12), 5582-5636; DOI: 10.1021/acs.chemrev.9b00638
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:102942
Deposited By: George Porter
Deposited On:01 May 2020 15:22
Last Modified:15 Feb 2022 18:09

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