Article | Published:

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

Nature Chemistry volume 1, pages 302309 (2009) | Download Citation

  • 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.

  • Compound C13H8ClN

    10-Chlorobenzo[h]quinoline

  • Compound C13H9N

    Benzo[h]quinoline

  • Compound C16H22O4

    α,α,α',α'-Tetramethyl-1,3-benzenedipropionic acid

  • Compound C15H11NO2

    Benzo[h]quinolin-10-yl acetate

  • Compound C15H8D3NO2

    Benzo[h]quinolin-10-yl acetate-d3

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

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.

References

  1. 1.

    Handbook of Organopalladium Chemistry for Organic Synthesis (John Wiley, 2002).

  2. 2.

    & Practical palladium catalysts for C–N and C–O bond formation. Top. Curr. Chem. 219, 131–209 (2002).

  3. 3.

    Carbon–heteroatom bond-forming reductive eliminations of amines, ethers, and sulfides. Acc. Chem. Res. 31, 852–860 (1998).

  4. 4.

    , , & Crystal and molecular structure of bis-μ-(bisdiphenylphosphinomethane)-dibromodipalladium(Pd–Pd), a compound containing palladium(I). J. Chem. Soc. Chem. Commun. 485–486 (1976).

  5. 5.

    & Organopalladium complexes containing palladium–palladium bonds. Coord. Chem. Rev. 231, 207–228 (2002).

  6. 6.

    et al. Experimental and theoretical investigations of new dinuclear palladium complexes as precatalysts for the amination of aryl chlorides. J. Am. Chem. Soc. 128, 6376–6390 (2006).

  7. 7.

    , , , & Palladium-catalyzed allylic substitution: reversible formation of allyl-bridged dinuclear palladium(I) complexes. Angew. Chem. Int. Ed. 46, 5892–5895 (2007).

  8. 8.

    Development of organopalladium(IV) chemistry: fundamental aspects and systems for studies of mechanism in organometallic chemistry and catalysis. Acc. Chem. Res. 25, 83–90 (1992).

  9. 9.

    , , & Carbon–oxygen bond formation at organopalladium centers: the reactions of PdMeR(L2) (R = Me, 4-tolyl; L2 = tmeda, bpy) with diaroyl peroxides and the involvement of organopalladium(IV) species. Organometallics 23, 1122–1131 (2004).

  10. 10.

    , , , & Carbon–oxygen bond formation at metal(IV) centers: reactivity of palladium(II) and platinum(II) complexes of the [2,6-(dimethylaminomethyl)phenyl-N,C,N] (pincer) ligand toward iodomethane and dibenzoyl peroxide; structural studies of M(II) and M(IV) complexes. Organometallics 23, 5432–5439 (2004).

  11. 11.

    , & Unusually stable palladium(IV) complexes: detailed mechanistic investigation of C–O bond-forming reductive elimination. J. Am. Chem. Soc. 127, 12790–12791 (2005).

  12. 12.

    & Reactivity of Pd(II) complexes with electrophilic chlorinating reagents: isolation of Pd(IV) products and observation of C–Cl bond-forming reductive elimination. J. Am. Chem. Soc. 129, 15142–15143 (2007).

  13. 13.

    & Carbon–fluorine reductive elimination from a high-valent palladium fluoride. J. Am. Chem. Soc. 130, 10060–10061 (2008).

  14. 14.

    The homogeneous palladium-catalyzed ortho-chlorination of azobenzene. J. Chem. Soc. Chem. Commun. 417 (1970).

  15. 15.

    , , & Palladium(II) acetate catalyzed aromatic substitution reaction. J. Org. Chem. 46, 1757–1759 (1981).

  16. 16.

    & Pd(II) catalyzed acetoxylation of arenes with iodosyl acetate. J. Mol. Catal. A: Chem. 108, 35–40 (1996).

  17. 17.

    , & A highly selective catalytic method for the oxidative functionalization of C–H bonds. J. Am. Chem. Soc. 126, 2300–2301 (2004).

  18. 18.

    , , & Oxidative C–H activation/C–C bond forming reactions: synthetic scope and mechanistic insights. J. Am. Chem. Soc. 127, 7330–7331 (2005).

  19. 19.

    , & Palladium-catalyzed fluorination of carbon–hydrogen bonds. J. Am. Chem. Soc. 128, 7134–7135 (2006).

  20. 20.

    , , & A simple catalytic method for the regioselective halogenation of arenes. Org. Lett. 8, 2523–2526 (2006).

  21. 21.

    , & Platinum model studies for palladium-catalyzed oxidative functionalization of C–H bonds. Organometallics 24, 482–485 (2005).

  22. 22.

    & Reactions of platinum(II) complexes with chloride-based oxidants: routes to Pt(III) and Pt(IV) products. Organometallics 27, 1683–1689 (2008).

  23. 23.

    , & Highly regioselective catalytic oxidative coupling reactions: synthetic and mechanistic investigations. J. Am. Chem. Soc. 128, 14047–14049 (2006).

  24. 24.

    , & Palladium-mediated fluorination of arylboronic acids. Angew. Chem. Int. Ed. 47, 5993–5996 (2008).

  25. 25.

    , & Silver-mediated fluorination of functionalized aryl stannanes. J. Am. Chem. Soc. 131, 1662–1663 (2009).

  26. 26.

    , , & Scope and selectivity in palladium-catalyzed directed C–H bond halogenation reactions. Tetrahedron 62, 11483–11498 (2006).

  27. 27.

    & Formation of covalent bonds from platinum or palladium to carbon by direct substitution. J. Am. Chem. Soc. 87, 3272–3273 (1965).

  28. 28.

    Cyclopalladated complexes in organic synthesis. Synthesis 233–252 (1985).

  29. 29.

    , & Cyclometallation. Palladium 2-arylpyridine complexes. J. Organomet. Chem. 202, 341–350 (1980).

  30. 30.

    , , , & Searching for precursors to metal–metal bonded dipalladium species: a study of Pd2(4+) complexes. Inorg. Chem. 44, 6129–6137 (2005).

  31. 31.

    et al. High yield syntheses of stable, singly bonded Pd2(6+) compounds. J. Am. Chem. Soc. 128, 13674–13675 (2006).

  32. 32.

    Measurement of formal potential of iodobenzene dichloride–iodobenzene couple in glacial acetic acid. Curr. Sci. 44, 662–663 (1975).

  33. 33.

    et al. A fractional bond order of 1/2 in Pd2(5+) formamidinate species; the value of very high-field EPR spectra. J. Am. Chem. Soc. 129, 1393–1401 (2007).

  34. 34.

    , , , & Synthesis and X-ray structural characterization of two unbridged diplatinum(III) compounds: cis- and trans-bis(bis(1-imino-1-methoxyethane)trichloroplatinum(III)). Transient species in the oxidation of platinum(II) to platinum(IV). J. Am. Chem. Soc. 119, 10370–10376 (1997).

  35. 35.

    , & Oxidative addition of S–S bonds to dimethylplatinum(II) complexes: evidence for a binuclear mechanism. Organometallics 27, 6521–6530 (2008).

  36. 36.

    Metal-mediated formation of carbon–halogen bonds. Chem. Eur. J. 14, 5102–5108 (2001).

  37. 37.

    & Reductive elimination of aryl halides from palladium(II). J. Am. Chem. Soc. 123, 1232–1233 (2001).

  38. 38.

    & Directly observed reductive elimination of aryl halides from monomeric arylpalladium(II) halide complexes. J. Am. Chem. Soc. 125, 13944–13945 (2003).

  39. 39.

    , , & Hydrogenolysis of palladium(II) hydroxide and methoxide pincer complexes. J. Am. Chem. Soc. 131, 1346–1347 (2009).

  40. 40.

    , , & Kinetics and thermodynamics of the reversible reaction between carbon monoxide and palladium(I) dimers containing bis(diphenylphosphino)methane. Organometallics 3, 1360–1364 (1984).

  41. 41.

    , , & Crystallographic characterization of the palladium(I) dimers, syn-Pd2Cl2(dppmMe)2 and Pd2Cl2(dppm)2; solution conformational behavior of syn- and anti-Pd2Cl2(dppmMe)2 and their (µ-Se) adducts [pddmMe = µ-1,1-bis(diphenylphosphino)ethane, and dppm = µ-bis(diphenylphosphino)methane]. Inorg. Chim. Acta 327, 179–187 (2002).

  42. 42.

    , , & Du Bois, J. Expanding the scope of C–H amination through catalyst design. J. Am. Chem. Soc. 126, 15378–15379 (2004).

  43. 43.

    , , , & Dirhodium(II) carboxylate complexes as building blocks. Cis-chelating dicarboxylic acids designed to bridge the dinuclear core. New J. Chem. 28, 425–433 (2004).

  44. 44.

    & Dinuclear reductive eliminations. Organometallics 3, 370–380 (1984).

  45. 45.

    & Reductive elimination of ethane from five-coordinate platinum(IV) alkyl complexes. Inorg. Chem. 46, 8496–8498 (2007).

  46. 46.

    et al. Mechanistic information on the reductive elimination from cationic trimethylplatinum(IV) complexes to form carbon–carbon bonds. Inorg. Chem. 44, 7732–7742 (2005).

  47. 47.

    Thermodynamics, kinetics, and mechanism of exchange of cyclopalladated ligands. Inorg. Chem. 26, 1252–1260 (1987).

Download references

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.

Author information

Affiliations

  1. Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts, USA

    • David C. Powers
    •  & Tobias Ritter

Authors

  1. Search for David C. Powers in:

  2. Search for Tobias Ritter in:

Contributions

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.

Corresponding author

Correspondence to Tobias Ritter.

Supplementary information

PDF files

  1. 1.

    Supplementary information

    Supplementary information

Crystallographic information files

  1. 1.

    Supplementary information

    Crystallographic data for compound 1

  2. 2.

    Supplementary information

    Crystallographic data for compound 2

  3. 3.

    Supplementary information

    Crystallographic data for compound 4a

  4. 4.

    Supplementary information

    Crystallographic data for compound 9

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/nchem.246

Further reading