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Cooperative carbon-atom abstraction from alkenes in the core of a pentanuclear nickel cluster

Nature Chemistry volume 9, pages 1282–1285 (2017)Cite this article

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Abstract

Although the cleavage of C–C bonds in unactivated hydrocarbons by soluble transition-metal complexes remains a challenge, such reactions hold the potential to provide access to previously inconceivable skeletal transformations. For instance, one can imagine the dismantling and reassembly of C–C and C–H bonds commonly observed in surface catalysis, but with the increased control innate to homogeneous catalysis. Here we report a pentanuclear nickel cluster that is unreactive to functional groups, such as alcohols, amines and even water, but selectively cleaves the C=C bonds of simple alkenes, such as ethylene, styrene and isobutylene, at temperatures as low as −30 °C and in near-quantitative yields. The isolation of intermediates in reactions with styrene and isobutylene demonstrates that the five nickel centres cooperatively activate three C–H bonds of the alkene substrate before cleaving the C–C bond in the core of the cluster to give a pentanuclear nickel carbide. The net organic product transformation is the abstraction of a carbon atom from an alkene.

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Figure 1: Cooperative carbon-atom abstraction from alkenes by [(iPr3P)Ni]5H6 (1).
Figure 2: ORTEP depiction of the solid-state molecular structure of 2, with 50% probability ellipsoids.
Figure 3: ORTEP depiction of the solid-state molecular structure of 3, with 50% probability ellipsoids.
Figure 4: ORTEP depiction of the solid-state structure of cluster 4, with 50% probability ellipsoids.

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Acknowledgements

Acknowledgement is made to the Natural Sciences and Engineering Research Council (NSERC) of Canada for funding. M.M.S. acknowledges the NSERC scholarship support.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, University of Windsor, Sunset Avenue 401, Windsor, N9B 3P4, Ontario, Canada

    Manar M. Shoshani & Samuel A. Johnson

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  1. Manar M. Shoshani
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Contributions

M.M.S. conducted the experiments and analysed the data. M.M.S. and S.A.J. conceived and designed the project and prepared the manuscript

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Correspondence to Samuel A. Johnson.

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The authors declare no competing financial interests.

Supplementary information

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Supplementary information (PDF 2034 kb)

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Crystallographic data for compound 2 (CIF 3129 kb)

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Crystallographic data for compound 3 (CIF 3070 kb)

Supplementary information

Crystallographic data for compound 4 (CIF 49 kb)

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Shoshani, M., Johnson, S. Cooperative carbon-atom abstraction from alkenes in the core of a pentanuclear nickel cluster. Nature Chem 9, 1282–1285 (2017). https://doi.org/10.1038/nchem.2840

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