An air-stable binary Ni(0)–olefin catalyst

Abstract

Nickel catalysis has become a growing and empowering area of research in recent years, providing new reactivity modes towards organic synthesis. In these endeavours, Ni(COD)2 (bis(1,5-cyclooctadiene)Ni(0)) vastly dominated this area, thus becoming the main source of Ni(0) for exploring new catalytic reactivity. However, all known Ni(0)–olefin precatalysts suffer from great instability and fast decomposition when exposed to air. With the aim of providing fast and facile technologies for practitioners, herein we report the synthesis, characterization and reactivity of an air stable binary Ni(0)–olefin complex, Ni(Fstb)3. This 16-electron complex features a unique arrangement of simple ligands that shield the nickel centre from oxygen. We demonstrate that Ni(Fstb)3 is an excellent precatalyst in a wide variety of important nickel-catalysed transformations and has unexpected catalytic properties compared with other Ni(0)–olefin complexes. As a general, practical and air-stable Ni(0) precursor, Ni(Fstb)3 represents a solution to a 60-year quest.

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Fig. 1: Ni(0) catalysts.
Fig. 2: Complexes 1 and 2.
Fig. 3: Ligand exchange of complex 2 with different ligands.
Fig. 4: Catalytic properties of 2 in a variety of nickel-catalysed transformations.
Fig. 5: Avoiding deactivation pathways.

Data availability

The Supplementary Information contains all experimental procedures and analytical data (1H, 19F, 31P, 13C NMR, high-resolution mass spectrometry elemental analysis and crystallographic data) for all of the new compounds. Crystallographic data for compounds 1 (CCDC: 1944830), 2 (CCDC: 1944831), 4 (CCDC: 1944832), 5 (CCDC: 1944833), 6 (CCDC: 1944834) and 7 (CCDC: 1944835) can be downloaded free of charge from the Cambridge Crystallographic Data Centre (www.ccdc.cam.ac.uk).

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Acknowledgements

Financial support for this work was provided by Max-Planck-Gesellschaft, Max-Planck-Institut für Kohlenforschung and Fonds der Chemischen Industrie (FCI-VCI). R.S. thanks the Ludwig-Maximilians University of Munich for the “Fakultäts-Unterstützung zur individuellen Studiengestaltung”. We thank S. Lutz and J. Busch for help in the preparation of Ni(CDT). We are thankful to M. Leutzsch for help in the NMR and R. Goddard for X-Ray support and proofreading the manuscript. We also thank A. Fürstner for insightful discussions and generous support.

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Contributions

L.N. designed the approach and performed the experiments, analysed the experimental data and prepared the Supplementary Information. R.S. expanded the applicability of the catalyst to a variety of nickel-catalysed transformations. N.N. analysed and acquired the crystallographic data of the nickel complexes. J.C. directed the investigations and prepared the manuscript.

Corresponding author

Correspondence to Josep Cornella.

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A patent disclosing the synthesis, characterization and application of the catalysts has been filed (patent no. EP19189236.3, Germany).

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Supplementary information

Supplementary Information

Supplementary methods and references

Compound 1

Crystallographic data for compound 1

Compound 2

Crystallographic data for compound 2

Compound 4

Crystallographic data for compound 4

Compound 5

Crystallographic data for compound 5

Compound 6

Crystallographic data for compound 6

Compound 7

Crystallographic data for compound 7

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Nattmann, L., Saeb, R., Nöthling, N. et al. An air-stable binary Ni(0)–olefin catalyst. Nat Catal 3, 6–13 (2020). https://doi.org/10.1038/s41929-019-0392-6

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