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Bimetallic Pd(III) complexes in palladium-catalysed carbon–heteroatom bond formation

A Corrigendum to this article was published on 01 August 2009

This article has been updated

Abstract

Palladium is a common transition metal for catalysis, and the fundamental organometallic reactivity of palladium in its 0, I, II and IV oxidation states is well established. The potential role of Pd(III) in catalysis has not been investigated because organometallic reactions that involve Pd(III) have not been reported previously. In this article we present the formation of carbon–heteroatom bonds from discrete bimetallic Pd(III) complexes and show the synergistic involvement of two palladium atoms of the bimetallic core during both oxidation and reductive elimination. Our results challenge the currently accepted mechanism for oxidative palladium catalysis via Pd(II)–Pd(IV) redox cycles and implicate bimetallic palladium complexes in redox catalysis. The new mechanistic insight provides an opportunity to explore rationally the potential of bimetallic palladium catalysis for synthesis.

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Figure 1: Two-electron oxidation and bimetallic reductive elimination.
Figure 2: Two-electron oxidation of 1 to give Pd(III)–Pd(III) complex 2 followed by bimetallic reductive elimination.
Figure 3: Mechanistic alternatives for reductive elimination from 2.
Figure 4: Reductive elimination from esp-derived bimetallic Pd(III)Cl (8).
Figure 5: Carbon–oxygen bond formation and pre-equilibrium acetate dissociation.
Figure 6: Bimetallic palladium complexes during catalysis.
Figure 7: Proposed catalytic cycle for carbon–heteroatom bond formation via bimetallic Pd(III) complexes.

Change history

  • 24 June 2009

    In the version of this article originally published, corrections were needed to some units and values of thermodynamic parameters: (1) page 303, penultimate sentence of column 1 should read: (ΔS) = −11.2 ± 9.4 cal K-1; (2) page 305, top of column 2 should read: (ΔG298 = 20.3 ± 0.1 kcal mol-1, ΔH = 23.4 ± 3.4 kcal mol-1, and ΔS = 10.2 ± 11.4 cal K-1). The authors wish to confirm that the corrections have no implications for their conclusions or the mechanistic proposal they have put forward. These changes have now been corrected on the HTML and PDF versions of this article.

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Acknowledgements

We thank T. A. Betley for DFT calculations, E. N. Jacobsen and D. G. Nocera, as well as I. Bae, for discussions, Merck for unrestricted support, Sanofi-Aventis for a graduate fellowship for DCP, T. Furuya, J. Y. Wu and D. M. Ho for crystallographic analysis and E. King for electrochemical analysis and DFT calculations.

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D.C.P. and T.R. conceived and designed the experiments, D.C.P. performed the experiments and D.C.P. and T.R. co-wrote the paper.

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Correspondence to Tobias Ritter.

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Crystallographic data for compound 1 (CIF 23 kb)

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Crystallographic data for compound 2 (CIF 30 kb)

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Crystallographic data for compound 4a (CIF 32 kb)

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Crystallographic data for compound 9 (CIF 39 kb)

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Powers, D., Ritter, T. Bimetallic Pd(III) complexes in palladium-catalysed carbon–heteroatom bond formation. Nature Chem 1, 302–309 (2009). https://doi.org/10.1038/nchem.246

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