Kinetics and Catalysis

, 50:676 | Cite as

Synthesis and reactivity of trimethylsilyl substituted mono(cyclopentadienyl)titanium alkyl complexes

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Abstract

The preparation of a series of titanium half-sandwich compounds [Ti(η5-C5H5−x(SiMe3)xR3] (x = 1–3, R = Cl, Me) and their reactivity for propene polymerization is reported. The compounds 1–3 polymerize propene, albeit in a much lower activity than the reported [Ti(η5-C5Me5Me3]/B(C6F5)3 catalyst. Unlike the reported [Ti(η5-C5Me5Me3]/B(C6F5)3 catalyst, the quasi living polymerization was not observed. Instead, we observe rather unusual temperature effects when the trityl salt [Ph3C][B(C6F5)4] was used as activator. The activity increases with increasing temperature, whereas when B(C6F5)3 is used a decrease is observed The rather broad (>2) PDI indicates multisite catalysts, and 13C-NMR indicates predominantly atactic polypropene. The solid state structure of the hydrolysis product [{Ti(η5-C5H4(SiMe3)Cl2}O] (4) was determined.

References

  1. 1.
    Ziegler, K., Holzkamp, E., Breil, H., and Martin, H., Angew. Chem., 1955, vol. 67, p. 541.CrossRefGoogle Scholar
  2. 2.
    Aulbach, M., Küber, F., Chem. Unserer Zeit., 1994, vol. 28, p. 197.CrossRefGoogle Scholar
  3. 3.
    Bochmann, M., J. Chem. Soc., Dalton Trans., 1996, p. 255.Google Scholar
  4. 4.
    Bochmann, M., Top. Catal, 1999, vol. 7, p. 9.CrossRefGoogle Scholar
  5. 5.
    Brintzinger, H.-H. and Fischer, D., Mühlhaupt, R., Rieger, B., and Waymouth, R., Angew. Chem., 1995, vol. 107, p. 1255.CrossRefGoogle Scholar
  6. 6.
    Jordan, R.F., Adv. Organomet. Chem., 1991, vol. 32, p. 325.CrossRefGoogle Scholar
  7. 7.
    Kaminsky, W. and Arndt, M., Adv. Polym. Sci., 1995, vol. 127, p. 144.Google Scholar
  8. 8.
    Rempel, G.L. and Huang, J., Prog. Polym. Sci., 1995, vol. 20, p. 459.CrossRefGoogle Scholar
  9. 9.
    Bochmann, M., J. Organomet. Chem., 2004, vol. 689, p. 3982.CrossRefGoogle Scholar
  10. 10.
    Kaminsky, W., J. Polym. Sci., Part A: Polym. Chem., 2004, vol. 16, p. 3911.CrossRefGoogle Scholar
  11. 11.
    Song, F., Lancaster, S.J., Cannon, R.D., Schormann, M., Humphrey, S.M., Zuccacia, C., Macchioni, A., and Bochmann, M., Organometallics, 2005, vol. 24, p. 1315.CrossRefGoogle Scholar
  12. 12.
    Macchioni, A., Chem. Rev., 2005, vol. 105, p. 2039.CrossRefGoogle Scholar
  13. 13.
    Britovsek, G.J.P., Gibson, V.C., and Wass, D.F., Angew. Chem., Int. Ed. Engl., 1999, vol. 38, p. 428.CrossRefGoogle Scholar
  14. 14.
    Small, B.L., Brookhart, M., and Bennet, A.M.A., J. Am. Chem. Soc., 1998, vol. 120, p. 4040.Google Scholar
  15. 15.
    Small, B.L. and Brookhart, M., Macromolecules, 1999, vol. 32, p. 2120.CrossRefGoogle Scholar
  16. 16.
    Deckers, P.J.W., van der Linden, A.J., Meetsma, A., and Hessen, B., Eur. J. Inorg. Chem., 2000, p. 929.Google Scholar
  17. 17.
    Deckers, P.J.W. and Hessen, B., Organometallics, 2002, vol. 21, p. 5564.CrossRefGoogle Scholar
  18. 18.
    Hessen, B., J. Mol. Catal. A: Chem., 2004, vol. 213, p. 129.CrossRefGoogle Scholar
  19. 19.
    Saßmannshausen, J., Powell, A.K., Anson, C.E., Wocadlo, S., and Bochmann, M., J. Organomet. Chem., 1999, vol. 592, p. 84.CrossRefGoogle Scholar
  20. 20.
    Saßmannshausen, J., Organometallics, 2000, vol. 19, p. 482.CrossRefGoogle Scholar
  21. 21.
    Bochmann, M., Robinson, O.B., Lancaster, S.J., Hursthouse, M.B., and Coles, S.J., Organometallics, 1995, vol. 14, p. 2456.CrossRefGoogle Scholar
  22. 22.
    Gillis, D.J., Tudoret, M.J., and Baird, M.C., J. Am. Chem. Soc., 1993, vol. 115, p. 2543.CrossRefGoogle Scholar
  23. 23.
    Gillis, D.J., Quyoum, R., Tudoret, M.J., Wang, Q., Jeremic, D., Roszak, A.W., and Baird, M.C., Organometallics, 1996, vol. 15, p. 3600.CrossRefGoogle Scholar
  24. 24.
    Jeremic, D., Wang, Q., Quyoum, R., and Baird, M.C., J. Organomet. Chem., 1995, vol. 497, p. 143.CrossRefGoogle Scholar
  25. 25.
    Wang, Q., Gillis, D.J., Quyoum, R., Jeremic, D., Tudoret, M.-J., and Baird, M.C., J. Organomet. Chem., 1997, vol. 527, p. 7.CrossRefGoogle Scholar
  26. 26.
    Wang, Q., Quyoum, R., Gillis, D.J., Tudoret, M.-J., Jeremic, D., Hunter, B.K., and Baird, M.C., Organometallics, 1996, vol. 15, p. 693.CrossRefGoogle Scholar
  27. 27.
    Tremblay, T.L., Ewart, S.W., Sarsfield, M.J., and Baird, M.C., Chem. Commun., 1997, p. 831.Google Scholar
  28. 28.
    Sarsfield, M.J., Ewart, S.W., Tremblay, T.L., Roszak, A.W., and Baird, M.C., J. Chem. Soc., Dalton Trans., 1997, p. 3097.Google Scholar
  29. 29.
    Flores, J.C., Wood, J.S., Chien, J.C.W., and Rausch, M.D., Organometallics, 1996, vol. 15, p. 4944.CrossRefGoogle Scholar
  30. 30.
    Pellecchia, C., Immirzi, A., Grassi, A., and Zambelli, A., Organometallics, 1993, vol. 12, p. 4473.CrossRefGoogle Scholar
  31. 31.
    Carr, A.G., Dawson, D.M., and Bochmann, M., Macromolecules, 1998, vol. 31, p. 2035.CrossRefGoogle Scholar
  32. 32.
    Eckstein, A., Suhm, J., Friedrich, C., Maier, R.D., Saßmannshausen, J., Bochmann, M., and Mülhaupt, R., Macromolecules, 1998, vol. 31, p. 1335.CrossRefGoogle Scholar
  33. 33.
    Saßmannshausen, J., Bochmann, M., Rosch, J., and Lige, D., J. Organomet. Chem., 1997, vol. 548, p. 23.CrossRefGoogle Scholar
  34. 34.
    Bochmann, M., Green, M.L.H., Powell, A.K., Saßmannshausen, J., Triller, M.U., and Wocadlo, S., J. Chem. Soc., Dalton Trans., 1999, p. 43.Google Scholar
  35. 35.
    Buhl, M. and Saßmannshausen, J., J. Chem. Soc., Dalton Trans., 2001, p. 79.Google Scholar
  36. 36.
    Doerrer, L.H., Green, M.L.H., Hüßinger, D., and Saßmannshausen, J., J. Chem. Soc., Dalton Trans., 1999, p. 2111.Google Scholar
  37. 37.
    Saßmannshausen, J., Green, J.C., Stelzer, F., and Baumgartner, J., Organometallics, 2006, vol. 25, p. 2796.CrossRefGoogle Scholar
  38. 38.
    Saßmannshausen, J., Track, A., and Stelzer, F., Organometallics, 2006, vol. 25, p. 4427.CrossRefGoogle Scholar
  39. 39.
    Saßmannshausen, J., Track, A., and Diaz, T.A.D.S., Eur. J. Inorg. Chem., 2007, vol. 16, p. 2327.CrossRefGoogle Scholar
  40. 40.
    Okuda, J., Top. Curr. Chem., 1991, vol. 160, p. 97.Google Scholar
  41. 41.
    Gowik, P., Klapötke, T., and Pickardt, J., J. Organomet. Chem., 1990, vol. 393, p. 343.CrossRefGoogle Scholar
  42. 42.
    Thewalt, U. and Schomburg, D., J. Organomet. Chem., 1977, vol. 127, p. 169.CrossRefGoogle Scholar
  43. 43.
    Weiss, T., Bohme, U., Walfort, B., Rheinwald, G., and Lang, H., Organometallics, 2005, vol. 24, p. 2577.CrossRefGoogle Scholar
  44. 44.
    Jia, L., Yang, X., Stern, C.L., and Marks, T.J., Organometallics, 1997, vol. 16, p. 842.CrossRefGoogle Scholar
  45. 45.
    Bernskoetter, W.H., Pool, J.A., Lobkovsky, E., and Chirik, P.J., Organometallics, 2006, vol. 25, p. 1092.CrossRefGoogle Scholar
  46. 46.
    Lanza, G., Fragala, I.L., and Marks, T.J., J. Am. Chem. Soc., 1998, vol. 120, p. 8257.CrossRefGoogle Scholar
  47. 47.
    Beswick, C.L. and Marks, T.J., Organometallics, 1999, vol. 18, p. 2410.CrossRefGoogle Scholar
  48. 48.
    Chen, E.Y., X. and Marks T.J., Chem. Rev., 2000, vol. 100, p. 1391.CrossRefGoogle Scholar
  49. 49.
    Li, L., Stern, C.L., and Marks, T.J., Organometallics, 2000, vol. 19, p. 3332.CrossRefGoogle Scholar
  50. 50.
    Zuccaccia, C., Stahl, N.G., Macchioni, A., Chen, M.-C., Roberts, J.A., and Marks, T.J., J. Am. Chem. Soc., 2004, vol. 126, p. 1448.CrossRefGoogle Scholar
  51. 51.
    Chen, M.-C., Roberts, J.A.S., Seyam, A.M., Li, L., Zuccaccia, C., Stahl, N.G., and Marks, T.J., Organometallics, 2006, vol. 25, p. 2833.CrossRefGoogle Scholar
  52. 52.
    Wilson, P.A., Hannant, M.H., Wright, J.A., Cannon, R.D., and Bochmann, M., Marcomol. Symp., 2006, vol. 236, p. 100.CrossRefGoogle Scholar
  53. 53.
    SAINTPLUS: Software Reference Manual, Version 6.45, Madison, Wis.: Bruker AXS, 1997–2003.Google Scholar
  54. 54.
    Blessing, R.H., Acta Crystallogr., Sect. A: Fundam. Crystallogr., 1995, vol. 51, p. 33.CrossRefGoogle Scholar
  55. 55.
    SADABS, Version 2.1, Madison, Wis.: Bruker AXS, 1998.Google Scholar
  56. 56.
    Sheldrick, G.M., SHELX97 Programs for Crystal Structure Analysis (Release 97-2), Göttingen: Universität Göttingen, 1998.Google Scholar
  57. 57.
    Winter, C.H., Zhou, X.-X., Dobbs, D.A., and Heeg, M.J., Organometallics, 1991, vol. 10, p. 210.CrossRefGoogle Scholar
  58. 58.
    Lund, E.C. and Livinghouse, T., Organometallics, 1990, vol. 9, p. 2426.CrossRefGoogle Scholar
  59. 59.
    Okuda, J., Chem. Ber., 1990, vol. 123, p. 87.CrossRefGoogle Scholar

Copyright information

© Pleiades Publishing, Ltd. 2009

Authors and Affiliations

  1. 1.Department of Pure and Applied ChemistryUniversity of StrathclydeSt. GlasgowUK
  2. 2.Institute of Inorganic ChemistryTU-GrazGrazAustria

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