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Metallacyclic actinide catalysts for dinitrogen conversion to ammonia and secondary amines

Nature Chemistry volume 12, pages 654–659 (2020)Cite this article

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An Author Correction to this article was published on 14 May 2020

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Abstract

Chemists have spent over a hundred years trying to make ambient temperature/pressure catalytic systems that can convert atmospheric dinitrogen into ammonia or directly into amines. A handful of successful d-block metal catalysts have been developed in recent years, but even binding of dinitrogen to an f-block metal cation is extremely rare. Here we report f-block complexes that can catalyse the reduction and functionalization of molecular dinitrogen, including the catalytic conversion of molecular dinitrogen to a secondary silylamine. Simple bridging ligands assemble two actinide metal cations into narrow dinuclear metallacycles that can trap the diatom while electrons from an externally bound group 1 metal, and protons or silanes, are added, enabling dinitrogen to be functionalized with modest but catalytic yields of six equivalents of secondary silylamine per molecule at ambient temperature and pressure.

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Fig. 1: The activation, protonation and silylation of dinitrogen by M2(mTP)2 complexes 1 and 2.
Fig. 2: The structures of the rectangular metallacyclic complex 1, and the functionalized dinitrogen-containing complex 2.

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Data availability

The crystallographic datasets for the structures reported in this study have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 1829624 (1U), 1829625 (Ut-thf), 1829626 (1U-diox), 1829627 (1Th-diox), 1829628 (1Th-py), 1829629 (2U), 1829630 (3U), 1939159 (Th(Lt)2(THF)2), 1939157 (Th(LPh)2(py)2), 1939160 ([K(DME)]2[ThCl2(Lt)2]), 1940146 ([K(DME)]2[Th(OMe)2(Lt)2]), 1939874 ([K(DME)4]2[(µ-O){Th(LPh)2}2]), 1939158(U(L)2(THF)2), 1946809 ([K][U(OMe)(L)2]). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. All other data supporting the findings of this study and detailed experimental procedures and characterization of compounds are available in the Supplementary Information files, and in the depository https://doi.org/10.17632/nm46kr3cnd.1.

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Acknowledgements

We thank the University of Edinburgh, the EPSRC, the JSPS and the ERC for funding.

Author information

Author notes

  1. Polly L. Arnold, Tatsumi Ochiai & Francis Y. T. Lam

    Present address: Department of Chemistry, University of California, Berkeley, Berkeley, CA, USA

Authors and Affiliations

  1. EaStCHEM School of Chemistry, The University of Edinburgh, Edinburgh, UK

    Polly L. Arnold, Tatsumi Ochiai, Francis Y. T. Lam, Rory P. Kelly & Megan L. Seymour

  2. Université de Toulouse and CNRS, INSA, UPS, CNRS, UMR 5215, LPCNO, Toulouse, France

    Laurent Maron

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Contributions

T.O., F.Y.T.L., R.P.K. and M.L.S. carried out the experiments. L.M. carried out and analysed the DFT calculations. P.L.A. conceived and supervised the project. All authors analysed the data and contributed to the writing of the manuscript.

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Correspondence to Polly L. Arnold.

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The authors declare no competing interests.

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Supplementary information

Supplementary Information

Supplementary methods, Figs.1–41, Tables 1 and 2, refs. 1–6, optimized structures, Cartesian coordinates for the optimized structures, Raman data, UV–vis data and GC-MS data.

Crystallographic data

Crystallographic data for 1U. CCDC reference 1829624.

Crystallographic data

Crystallographic data for 1Ut-thf. CCDC reference 1829625.

Crystallographic data

Crystallographic data for 1U-diox. CCDC reference 1829626.

Crystallographic data

Crystallographic data for 1Th-diox. CCDC reference 1829627.

Crystallographic data

Crystallographic data for 1Th-py. CCDC reference 1829628.

Crystallographic data

Crystallographic data for 2U. CCDC reference 1829629.

Crystallographic data

Crystallographic data for 3U. CCDC reference 1829630.

Crystallographic data

Crystallographic data for Th(Lt)2(THF)2. CCDC reference 1939159.

Crystallographic data

Crystallographic data for Th(LPh)2(py)2. CCDC reference 1939157.

Crystallographic data

Crystallographic data for [K(DME)]2[ThCl2(Lt)2]. CCDC reference 1939160.

Crystallographic data

Crystallographic data for [K(DME)]2[Th(OMe)2(Lt)2]. CCDC reference 1940146.

Crystallographic data

Crystallographic data for [K(DME)4]2[(µ-O){Th(LPh)2}2]. CCDC reference 1939874.

Crystallographic data

Crystallographic data for U(L)2(THF)2. CCDC reference 1939158.

Crystallographic data

Crystallographic data for [K][U(OMe)(L)2]. CCDC reference 1946809.

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Arnold, P.L., Ochiai, T., Lam, F.Y.T. et al. Metallacyclic actinide catalysts for dinitrogen conversion to ammonia and secondary amines. Nat. Chem. 12, 654–659 (2020). https://doi.org/10.1038/s41557-020-0457-9

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