Homogeneous/heterogeneous palladium based catalytic system for Heck reaction. The reversible transfer of palladium between solution and support

Pd(II)/Al2O3 and Pd(0)/Al2O3, containing 0.6% of palladium were characterized by EDX, SEM and XRD methods and used as catalysts of the Heck coupling of bromobenzene with butyl acrylate at 140 °C in molten [Bu4N]Br salt. Monoarylated (trans-PhCH = CHC(O)OBu) (1) and diarylated (Ph2C = CHC(O)OBu) (2) products were obtained in amounts dependent on kind of base present in the system (Scheme 1). During the reaction palladium was partially leached from the support forming [Bu4N][PdBr4] complex that catalyze Heck reaction or undergo readsorption on Al2O3. These soluble palladium complexes are partially reduced to Pd soluble nanoparticles which can also be anchored on Al2O3 giving active catalyst of Pd(0)/Al2O3 type. Reduction of Pd(II) to Pd(0) during catalytic process at the presence of bases (NaHCO2, NaHCO3, NaOAc, Cs2CO3) was studied by XPS method and the total reduction was observed in reactions of PdCl2(PhCN)2 with NaHCO2 or with NaHCO3 and [Bu4N]Br. It was experimentally proved that heterogenized catalyst, Pd(0)/Al2O3, after oxidative addition of aryl halides, serve as a source of soluble palladium species and colloidal nanoparticles that are active as homogeneous catalysts.

This is a preview of subscription content, access via your institution.

References

  1. 1

    W.A. Herrmann, Applied homogeneous catalysis with organometallic compounds, in: A Comprehensive Handbook in Two Volumes, eds. B. Cornils, W.A. Herrmann (V. C. H. Weinheim, New York, 1996)

  2. 2

    Handbook of palladium catalyzed organic reactions. Synthetic aspects and catalytic cycles. J.-L. Malleron, J.-C. Fiaud, J.-Y. Legros, Academic Press, Harcout Brace & Company Publishers

  3. 3

    R.B. Bedford C.S.J. Cazin D Holder (2004) Coord. Chem. Rev. 248 2283 Occurrence Handle10.1016/j.ccr.2004.06.012 Occurrence Handle1:CAS:528:DC%2BD2cXhtVagsLzP

    Article  CAS  Google Scholar 

  4. 4

    A. Zapf, M. Beller, Chem. Commun. (2005) 431

  5. 5

    M. Beller B. Cornils C.D. Frohning C.W Kohlpaintner (1995) J. Mol. Catal. A: Chem. 104 17 Occurrence Handle10.1016/1381-1169(95)00130-1 Occurrence Handle1:CAS:528:DyaK2MXpsV2ks7k%3D

    Article  CAS  Google Scholar 

  6. 6

    R. Skoda -Foldes L Kollar (2002) Curr. Organic Chem. 6 1097 Occurrence Handle10.2174/1385272023373699 Occurrence Handle1:CAS:528:DC%2BD38Xmslyjtbs%3D

    Article  CAS  Google Scholar 

  7. 7

    K. Sonogashira in: Handbook of Organopalladium Chemistry for Organic Syntheses, ed. E. Negishi (Wiley & Sons, New York, 2002)

  8. 8

    N. Miyaura A. Suzuki (1995) Chem. Rev. 95 2457 Occurrence Handle10.1021/cr00039a007 Occurrence Handle1:CAS:528:DyaK2MXoslGiurg%3D

    Article  CAS  Google Scholar 

  9. 9

    R.F Heck (1979) Acc. Chem. Res. 12 146 Occurrence Handle10.1021/ar50136a006 Occurrence Handle1:CAS:528:DyaE1MXhsFWju7g%3D

    Article  CAS  Google Scholar 

  10. 10

    I.P. Beletskaya A.V. Cheprakov (2000) Chem. Rev. 100 3009 Occurrence Handle10.1021/cr9903048 Occurrence Handle1:CAS:528:DC%2BD3cXltVSitb8%3D

    Article  CAS  Google Scholar 

  11. 11

    N.J. Whitcombe K.K. Hii S.E. Gibson (2001) Tetraheron 57 7449 Occurrence Handle10.1016/S0040-4020(01)00665-2 Occurrence Handle1:CAS:528:DC%2BD3MXmtFGgsro%3D

    Article  CAS  Google Scholar 

  12. 12

    (a) W.A. Herrmann, M. Elison, J. Fischer, C. Köcher, G.R.J. Artus, Angew. Chem. Int. Ed. Engl. 34(21) (1995) 2371; (b) W.A. Herrmann, V.P.W. Böhm, J. Organomet. Chem. 572 (1999) 141; (c) V.P.W. Böhm, W.A. Herrmann, Chem. Eur. J. 7(19) (2001) 4191; (d) D. Morales-Morales, C. Grause, K. Kasaoka, R. Redon, R.E. Cramer, C.M. Jenson, Inorg. Chim. Acta 300–302 (2000) 958; (e) M. Ohff, A. Ohff, M. E. v. der Bomm, D. Milstein, J. Am. Chem. Soc. 119 (1997) 11687; (f) Y. Ben-David, M. Portnoy, M. Gozin, D. Milstein, Organomet. 11 (1992) 1995

  13. 13

    A.H.M. Vries ParticleDe J.M.C.A. Mulders J.H.M. Mommers H.J.W. Henderickx J.G. Vries ParticleDe (2003) Org. Lett. 5 IssueID18 3285 Occurrence Handle10.1021/ol035184b

    Article  Google Scholar 

  14. 14

    M.T. Reetz J.G. Vries Particlede (2004) Chem. Commun. 14 1559 Occurrence Handle10.1039/b406719n

    Article  Google Scholar 

  15. 15

    M.T. Reetz, G. Lohmer, Chem. Commun. (1996) 1921

  16. 16

    C. Luo Y. Zhang Y. Wang (2005) J. Mol. Catal. A Chem. 229 7 Occurrence Handle10.1016/j.molcata.2004.10.039 Occurrence Handle1:CAS:528:DC%2BD2MXht1CrsL4%3D

    Article  CAS  Google Scholar 

  17. 17

    J.-M. Basset F. Lefebre C. Santini (1998) Coord. Chem. Rev. 178 1703 Occurrence Handle10.1016/S0010-8545(98)00159-3

    Article  Google Scholar 

  18. 18

    T.H. Galow, U. Drechsler, J.A. Hanson, V.M. Rotello, Chem. Commun. (2002) 1076

  19. 19

    V.R. Batchu V. Subramanian K. Parasuraman N.K. Swamy S. Kumar M Pal (2005) Tetrahedron 61 9869 Occurrence Handle10.1016/j.tet.2005.06.056 Occurrence Handle1:CAS:528:DC%2BD2MXpvVSntbk%3D

    Article  CAS  Google Scholar 

  20. 20

    S. Daniel P. Prabhakara Rao M. Nandakumar T Prasada Rao (2005) Mater. Chem. Phys. 90 99 Occurrence Handle10.1016/j.matchemphys.2004.10.016 Occurrence Handle1:CAS:528:DC%2BD2cXhtVyrtL%2FM

    Article  CAS  Google Scholar 

  21. 21

    G.R. Cairns R.J. Cross D Stirling (2001) J. Mol. Catal. A Chem. 172 207 Occurrence Handle10.1016/S1381-1169(01)00116-9 Occurrence Handle1:CAS:528:DC%2BD3MXksFKksrY%3D

    Article  CAS  Google Scholar 

  22. 22

    S. Behrens, G. Spittel, Dalton Trans. (2005) 868

  23. 23

    C.P. Mehnert D.W. Weaver J.Y Ying (1998) J. Am. Chem. Soc. 120 12289 Occurrence Handle10.1021/ja971637u Occurrence Handle1:CAS:528:DyaK1cXnt1Clt70%3D

    Article  CAS  Google Scholar 

  24. 24

    L. Djakovitch M. Wagner C.G. Hartung M. Beller K. Koehler (2004) J. Mol. Catal. A Chem. 219 121 Occurrence Handle10.1016/j.molcata.2004.04.035 Occurrence Handle1:CAS:528:DC%2BD2cXls1Wrur0%3D

    Article  CAS  Google Scholar 

  25. 25

    I.W. Davies L. Matty D.L. Hughes P.J Reider (2001) J. Am. Chem. Soc. 123 10139 Occurrence Handle10.1021/ja016877v Occurrence Handle1:CAS:528:DC%2BD3MXmvFOmsbg%3D

    Article  CAS  Google Scholar 

  26. 26

    A.F. Shmidt L.V Mametova (1996) Kinet. Catal. 37 406

    Google Scholar 

  27. 27

    A. Biffis, M. Zecca, M. Basato, Eur. J. Chem. (2001) 1131

  28. 28

    K. Köhler R.G. Heidenreich J.G.E. Krauter J. Pietsch (2002) Chem. Eur. J. 8 IssueID3 622 Occurrence Handle10.1002/1521-3765(20020201)8:3<622::AID-CHEM622>3.0.CO;2-0

    Article  Google Scholar 

  29. 29

    S.S. Pröckl W. Kleist M.A. Gruber K. Köhler (2004) Angew. Chem. Int. Ed. 43 1881 Occurrence Handle10.1002/anie.200353473

    Article  Google Scholar 

  30. 30

    S.S. Pröckl W. Kleist K. Köhler (2005) Tetrahedron 61 9855 Occurrence Handle10.1016/j.tet.2005.06.111

    Article  Google Scholar 

  31. 31

    S. Jayasree, A. Seayad, R.V. Chaudhari, Chem. Commun. (1999) 1067

  32. 32

    F. Zhao K. Murakami M. Shirai M. Arai (2000) J. Catal. 194 479 Occurrence Handle10.1006/jcat.2000.2934 Occurrence Handle1:CAS:528:DC%2BD3cXmtVygsrg%3D

    Article  CAS  Google Scholar 

  33. 33

    A. Corma H. Garcia A. Leyva (2005) J. Mol. Catal. A Chem. 230 97 Occurrence Handle10.1016/j.molcata.2004.11.030 Occurrence Handle1:CAS:528:DC%2BD2MXhvVSktbk%3D

    Article  CAS  Google Scholar 

  34. 34

    A. Papp K. Miklos P. Forgo A. Molnar (2005) J. Mol. Catal. A: Chem. 229 107 Occurrence Handle10.1016/j.molcata.2004.11.011 Occurrence Handle1:CAS:528:DC%2BD2MXht1Crsbs%3D

    Article  CAS  Google Scholar 

  35. 35

    H. Hagiwara Y. Shimizu T. Hoshi T. Suzuki M. Ando K. Ohkubo C. Yokoyama (2001) Tetrahedron Lett. 42 4349 Occurrence Handle10.1016/S0040-4039(01)00748-1 Occurrence Handle1:CAS:528:DC%2BD3MXkt1Kjurs%3D

    Article  CAS  Google Scholar 

  36. 36

    M. Poyatos F. Marquez E. Peris C. Claver E. fernandez (2003) New J. Chem. 27 425 Occurrence Handle10.1039/b204911b Occurrence Handle1:CAS:528:DC%2BD3sXkvFegtw%3D%3D

    Article  CAS  Google Scholar 

  37. 37

    V. Calo A. Nacci A. Monopoli A. Fornaro L. Sabbatini N. Cioffi N. Ditaranto (2004) Organometals 23 5154 Occurrence Handle10.1021/om049586e Occurrence Handle1:CAS:528:DC%2BD2cXns1WitbY%3D

    Article  CAS  Google Scholar 

  38. 38

    A. Gniewek A.M. Trzeciak J.J. Ziółkowski L. Kępiński J. Wrzyszcz W Tylus (2005) J. Catal. 229 332 Occurrence Handle10.1016/j.jcat.2004.11.003 Occurrence Handle1:CAS:528:DC%2BD2MXht1Ojsrk%3D

    Article  CAS  Google Scholar 

  39. 39

    A.M. Trzeciak W. Wojtków J.J. Ziółkowski J. Wrzyszcz M Zawadzki (2004) New J. Chem. 28 859 Occurrence Handle10.1039/b401912a Occurrence Handle1:CAS:528:DC%2BD2cXlslCjtLc%3D

    Article  CAS  Google Scholar 

  40. 40

    F. Bertoux E. Monflier Y. Castanet A. Mortreux (1999) J. Mol. Catal. A Chem. 143 23 Occurrence Handle10.1016/S1381-1169(98)00359-8 Occurrence Handle1:CAS:528:DyaK1MXivFOmtLs%3D

    Article  CAS  Google Scholar 

  41. 41

    B. Yoon, H. Kim, C.M. Wai, Chem. Commun. (2003) 1041

  42. 42

    J. Wrzyszcz W. Miśta D. Hreniak W. Stręk M. Zawadzki H Grabowska (2002) J. Alloys Comp. 341 358 Occurrence Handle10.1016/S0925-8388(02)00037-3 Occurrence Handle1:CAS:528:DC%2BD38XkvF2jtLg%3D

    Article  CAS  Google Scholar 

  43. 43

    D.D. Perrin W.L.F. Armarego D.R. Perrin (1986) Purification of Laboratory Chemicals Pergamon Oxford, England

    Google Scholar 

  44. 44

    G.K. Andersen, M. Lin, Inorg. Syntheses, Vol. 28, ed. R.J. Angelici (John Wiley and Sons, Inc. 1990), p. 60

  45. 45

    J. Wrzyszcz, private communication

  46. 46

    V. Calo A. Nacci A. Monopoli L. Lopez A. Cosmo ParticleDi (2001) Tetrahedron 57 6071 Occurrence Handle10.1016/S0040-4020(01)00528-2 Occurrence Handle1:CAS:528:DC%2BD3MXkvFOrtro%3D

    Article  CAS  Google Scholar 

  47. 47

    J. Le Bras D.K. Mukherjee S. Gonzáles M. Tristany B. Ganchegui M. Moreno-Manas R. Pleixats F. Hénin J. Muzart (2004) New. J. Chem. 28 1550 Occurrence Handle10.1039/b409604e Occurrence Handle1:CAS:528:DC%2BD2cXhtVGqurvN

    Article  CAS  Google Scholar 

Download references

Author information

Affiliations

Authors

Corresponding author

Correspondence to Anna M. Trzeciak.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Pryjomska-Ray, I., Gniewek, A., Trzeciak, A.M. et al. Homogeneous/heterogeneous palladium based catalytic system for Heck reaction. The reversible transfer of palladium between solution and support. Top Catal 40, 173–184 (2006). https://doi.org/10.1007/s11244-006-0119-1

Download citation

Keywords

  • Heck reaction
  • XPS
  • XRD
  • SEM
  • heterogenized catalyst
  • Pd colloid
  • Pd nanoparticles