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Assembling Ligand Substitution Reactions Monitored by VT 31P{H} NMR Spectroscopy In Order to Shine Light on the Mechanism of Formation of the Pd–Pd Bond-Containing {Pd2 (dmb)2(diphos)2+} n , {Pd2(diphos′)2 (dmb)2+} n and {Pd2 (dppm)2 (diphos)2+} n Coordination/Organometallic Polymers

  • Dalila Samar
  • Pierre D. Harvey
Article

Abstract

The mechanism of formation of the related polymers {Pd2(dmb)2(diphos)2+} n , {Pd2(diphos′)2(dmb)2+} n and {Pd2(dppm)2(diphos)2+} n (dmb = 1,8-diisocyano-p-menthane; diphos = bis(diphenylphosphino)butane (dppb), bis(diphenylphosphino)pentane (dpppen), bis(diphenylphosphino)hexane (dpph); diphos‘ = bis(diphenylphosphino)ethane (dppe), bis(diphenylphosphino)propane (dppp); dppm = bis(diphenylphosphino)methane) was investigated through the bridging ligand substitution reaction between the d9–d9 Pd2(dmb)2Cl2 complex and dppm by means of VT 31P{H} NMR spectroscopy in 1:1 CD3OD/CD2Cl2mixture (193 < T < 293 K) in the presence or absence of LiClO4 and TlPF6. The reaction proceeds with the appearance and disappearance of intermediates, all easily identified from spectral comparison with related authentic samples, hence allowing determining the stepwise mechanism towards substitution, a process that contains all the necessary steps for the formation of the title polymers. For the \({\{Pd_{2}(diphos^\prime)_{2}(dmb)^{2+}\}_{n}}\) polymers, which contains chelating diphosphines, this study indicates that the axial Cl-ligand must first dissociate to allow the primary P-coordination to form a η1-dppm-containing intermediate.

Keywords

Coordination polymers organometallic polymers mechanism of formation 31P NMR spectroscopy palladium Pd–Pd bond bis(diphenylphosphino)methane diisocyano-p-menthane 

Notes

Acknowledgments

NSERC is thanked for generous support for this research.

References

  1. 1.
    Han L., Hong M. (2005) Inorg Chem Commun. 8:406CrossRefGoogle Scholar
  2. 2.
    Ye Q., Wang X. -S., Zhao H., Xiong R. -G. (2005) Chem Soc Rev. 34:208CrossRefGoogle Scholar
  3. 3.
    Itaya T., Inoue K. (2002) Recent Research Developments in Macromolecules. 6:249Google Scholar
  4. 4.
    Uemura T., Kitagawa S. (2005) Chem Letters. 34:132CrossRefGoogle Scholar
  5. 5.
    Ye B.H., Tong M.-L., Chen X.-M. (2005) CoordChem Reviews. 249:545CrossRefGoogle Scholar
  6. 6.
    Kitagawa S., Uemura K. (2005) Chem Soc Reviews. 34:109CrossRefGoogle Scholar
  7. 7.
    Harvey P.D. (2004) J Inorg Organomet Poly. 14:211CrossRefGoogle Scholar
  8. 8.
    Abd-El-Aziz A.S., Okasha R.M., Todd E.K., Afifi T.H., Shipman P.O., Copping K.M.D. (2004) Macromol Symp. 209:185CrossRefGoogle Scholar
  9. 9.
    J.-C. Dai, Z.-Y. Fu, X.-T. Wu, in Encyclopedia of Nanoscience and Nanotechnology, H. S. Nalwa, ed. (American Scientific Publishers, Stevenson Ranch, Calif., 2004), Vol. 10, p. 247.Google Scholar
  10. 10.
    X. Chen, C. M. Drain, Encyclopedia of Nanoscience and Nanotechnology (American Scientific Publishers, Stevenson Ranch, Calif., 2004), Vol. 9, p. 593.Google Scholar
  11. 11.
    Knapp R., Kelch S., Schmelz O., Rehahn M. (2003) Macromol Symp. 204:267CrossRefGoogle Scholar
  12. 12.
    Kesanli B., Lin W. (2003) Coord Chem Reviews. 246:305CrossRefGoogle Scholar
  13. 13.
    Carlucci L., Ciani G., Proserpio D. M. (2003) Coord Chem Reviews. 246:247CrossRefGoogle Scholar
  14. 14.
    Erxleben A. (2003) Coord Chem Reviews. 246:203CrossRefGoogle Scholar
  15. 15.
    Zheng S. -L., Tong M. -L., Chen X. -M. (2003) Coord Chem Reviews. 246:185CrossRefGoogle Scholar
  16. 16.
    Barnett S. A., Champness N. R. (2003) Coord Chem Reviews. 246:145CrossRefGoogle Scholar
  17. 17.
    Abd-El-Aziz A. S., Todd E. K. (2003) Coord ChemReviews. 246:3CrossRefGoogle Scholar
  18. 18.
    Chivers T. (2003) Topics in Current Chemistry. 229:143Google Scholar
  19. 19.
    Batten S. R., Murray K. S. (2003) Coord Chem Reviews. 246:103CrossRefGoogle Scholar
  20. 20.
    D. Woehrle, in Metal Complexes and Metals in Macromolecules, D. Woehrle, A. D. Pomogailo eds. (Wiley-VCH, Weinheim, 2003), p. 279Google Scholar
  21. 21.
    Abd-El-Aziz A. S., Todd E. K. (2001) Polymer News. 26:5Google Scholar
  22. 22.
    Moulton B., Zaworotko M. J. (2002) Current Opinion in Solid State & Materials Science 6:117CrossRefGoogle Scholar
  23. 23.
    Liu Y., Li Y., Schanze K. S. (2002) J Photochem Photobio. C: Photochem Reviews. 3:1CrossRefGoogle Scholar
  24. 24.
    Andres P. R., Schubert U. S. (2004) Advanced Materials. 16:1043CrossRefGoogle Scholar
  25. 25.
    Tyler D. R., Chen R. (2004) Macromol Symp. 209:231CrossRefGoogle Scholar
  26. 26.
    Tomita I., Ueda M. (2004) Macromol Symp. 209:217–230CrossRefGoogle Scholar
  27. 27.
    Moorlag C., Clot O., Zhu Y., Wolf M. O. (2004) Macromol Symp. 209:133CrossRefGoogle Scholar
  28. 28.
    Tyler D. R. (2003) Coord Chem Reviews. 246:291CrossRefGoogle Scholar
  29. 29.
    Onitsuka K., Takahashi S. (2003) Topics in Current Chemistry. 228:39CrossRefGoogle Scholar
  30. 30.
    Nishihara H., Kurashina M., Murata M. (2003) Macromol Symp. 196:27CrossRefGoogle Scholar
  31. 31.
    Schubert U. S., Eschbaumer C. (2002) Angew Chem Int Ed. 41:2892CrossRefGoogle Scholar
  32. 32.
    Gates D. P. (2002) Annual Reports on the Progress of Chemistry Section A: Inorganic Chemistry. 98:479CrossRefGoogle Scholar
  33. 33.
    Harvey P. D. (2001) Coord Chem Rev. 219–221:17Google Scholar
  34. 34.
    Fournier É., Lebrun F., Drouin M., Decken A., Harvey P.D. (2004) Inorg Chem. 43:3127CrossRefGoogle Scholar
  35. 35.
    Zhang T., Drouin M., Harvey P.D. (1999) . Inorg Chem. 38:957CrossRefGoogle Scholar
  36. 36.
    Sicard S., Bérubé J. -F., Samar D., Messaoudi A., Lebrun F., Fortin J. -F., Fortin D., Harvey P. D. (2004) Inorg Chem. 435:321Google Scholar
  37. 37.
    Fournier É., Sicard S., Decken A., Harvey P. D. (2004) Inorg Chem. 43:1491CrossRefGoogle Scholar
  38. 38.
    J.-F. Bérubé, K. Gagnon, D. Fortin, A. Decken, P. D. Harvey, submitted 2005Google Scholar
  39. 39.
    Balch A. L., Benner L. S. (1982) Inorganic Syntheses 21:47CrossRefGoogle Scholar
  40. 40.
    Perreault D., Drouin M., Michel A., Harvey P. D. (1992) . Inorg Chem. 31:2740CrossRefGoogle Scholar
  41. 41.
    Weber W. P., Gokel G. W. (1972) Tetrahedron Lett. 17:1637CrossRefGoogle Scholar
  42. 42.
    Tiekink E. R. T. (1990) Acta Cryst. C46:235Google Scholar
  43. 43.
    Benner L. S., Balch A. L. (1978) J Am Chem Soc. 100:6099CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2007

Authors and Affiliations

  1. 1.Département de ChimieUniversité de SherbrookeSherbrookeCanada

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