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Exceptionally fast carbon–carbon bond reductive elimination from gold(III)

Nature Chemistry volume 6, pages 159–164 (2014)Cite this article

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An Addendum to this article was published on 22 April 2014

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Abstract

Reductive elimination of carbon–carbon bonds occurs in numerous metal-catalysed reactions. This process is well documented for a variety of transition metal complexes. However, carbon–carbon bond reductive elimination from a limited number of Au(III) complexes has been shown to be a slow and prohibitive process that generally requires elevated temperatures. Herein we show that oxidation of a series of mono- and bimetallic Au(I) aryl complexes at low temperature generates observable Au(III) and Au(II) intermediates. We also show that aryl–aryl bond reductive elimination from these oxidized species is not only among the fastest observed for any transition metal, but is also mechanistically distinct from previously studied alkyl–alkyl and aryl–alkyl reductive eliminations from Au(III).

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Figure 1: Oxidation of monometallic Au(I) and biaryl reductive elimination from Au(III).
Figure 2: Kinetics of decay of cis-(Ph3P)Au(4-F-C6H4)2Cl (3).
Figure 3: Unexpected phosphine acceleration on the decay of 3 at −52 °C.
Figure 4: Oxidation of bimetallic Au(I)/Au(I) complexes.
Figure 5: Monitoring oxidation of dppm[Au(4-F-C6H4)]2 (8) to Au(II)/Au(II) intermediate 8, isomerization to Au(I)/Au(III) species 10 and reductive elimination of 4,4′-difluorobiphenyl.
Figure 6: Five-atom linker dppp discourages formation of Au(II)/Au(II) intermediates on oxidation of bimetallic dppp[Au(4-F-C6H4)]2 (11).

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  • 22 April 2014

    In our Article we described the preparation and observation in situ of a complex of the type [Au(aryl)2Cl(PPh3)], which is similar to a series of cyclometallated Au(iii) complexes that undergo aryl–aryl and aryl–alkyl reductive elimination reported in two papers that we inadvertently omitted from our reference list: Vicente, J., Bermudez, M. D., Escribano, J., Carrillo, M. P. & Jones, P. G. Synthesis of intermediates in the C–H activation of acetone with 2-phenylazophenylgold(iii) complexes and in the C–C coupling of aryl groups from diarylgold(iii) complexes. Crystal and molecular structures of [Au{C6H3(N=NC6H4Me-4')-2-Me-5}(acac-C)Cl](acac = acetylacetonate), cis-[Au(C6H4N=NPh-2)Cl2(PPh3)] and [Au(C6H4CH2NMe2-2)(C6F5)Cl]. J. Chem. Soc. Dalton Trans. 3083–3089 (1990). Vicente, J., Bermudez, M. D. & Escribano, J. Gold in organic synthesis. preparation of symmetrical and unsymmetrical biaryls via C–C coupling from cis-diarylgold(iii) complexes. Organometallics 10, 3380–3384 (1991).

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Acknowledgements

This research was supported in part by a grant from the National Institutes of Health (NIH) General Medical Sciences (RO1 GM073932). We thank the National Science Foundation (predoctoral fellowship to W.J.W., grant no. DGE 1106400) and NIH (postdoctoral fellowship to M.S.W., grant no. F32 GM103238-02) for funding. We thank R. G. Bergman, N. P. Mankad and M. D. Levin for helpful discussions, and A. DiPasquale for crystallographic assistance.

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  1. William J. Wolf and Matthew S. Winston: These authors contributed equally to this work

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  1. Department of Chemistry, University of California, Berkeley, 94720, California, USA

    William J. Wolf, Matthew S. Winston & F. Dean Toste

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Contributions

M.S.W. and W.J.W. conceived, designed and performed the experiments, analysed the data and wrote the manuscript; M.S.W. derived kinetic models; W.J.W. performed the crystallographic analysis. F.D.T. supervised the project.

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Correspondence to F. Dean Toste.

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Supplementary information (PDF 2613 kb)

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Crystallographic data for compound 5. (CIF 24 kb)

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Crystallographic data for compound 8. (CIF 19 kb)

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Crystallographic data for compound 11. (CIF 19 kb)

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Wolf, W., Winston, M. & Toste, F. Exceptionally fast carbon–carbon bond reductive elimination from gold(III). Nature Chem 6, 159–164 (2014). https://doi.org/10.1038/nchem.1822

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