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Ziegler–Natta catalyst activation. Thermodynamic and kinetic aspects of metallocenium ion-pair formation, dissociation, and structural reorganization

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Abstract

This contribution reviews thermochemical and dynamic NMR studies of metallocenium olefin polymerization catalyst formation from, and dissociation to, the neutral metallocene dimethyl precursors and either fluoroarylboranes or methylalumoxane (MAO), as well as the kinetics of ion pair separation/recombination/reorganization. Significant correlations are found between borane Lewis acidity, the enthalpy of catalyst formation, catalyst NMR spectral parameters, the free energy of activation of catalyst ion pair separation/recombination/reorganization, and ethylene polymerization activity.

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References

  1. R.F. Jordan, J. Mol. Catal. 128 (special issue) (1998) and references therein.

  2. W. Kaminsky and M. Arndt, Adv. Polymer Sci. 127 (1997) 144.

    Google Scholar 

  3. M. Bochmann, J. Chem. Soc., Dalton Trans. (1996) 255.

  4. H.H. Brintzinger, D. Fischer, R. M¨ulhaupt, B. Riger and R.M. Waymouth, Angew. Chem. Int. Ed. Engl. 34 (1995) 1143.

    Article  CAS  Google Scholar 

  5. A.A. Guram and R.F. Jordan, in: Comprehensive Organometallic Chemistry II, eds. E.W. Abel, F.G.A. Stone and G. Wilkinson (Elsevier, Oxford, 1995) ch. 12.

  6. Catalyst Design for Tailor-Made Polyolefins, eds. K. Soga and M. Terano (Elsevier, Tokyo, 1994).

  7. P.C. M¨ohring and N.J. Coville, J. Organomet. Chem. 479 (1994) 1.

    Article  Google Scholar 

  8. Y.-X. Chen, M.V. Metz, L. Li, C.L. Stern and T.J. Marks, J. Am. Chem. Soc. 120 (1998) 6287.

    Article  CAS  Google Scholar 

  9. L. Li and T.J. Marks, Organometallics 17 (1998) 3996.

    Article  CAS  Google Scholar 

  10. Y.-X. Chen and T.J. Marks, Organometallics 16 (1997) 3649.

    Article  CAS  Google Scholar 

  11. Y. Obora, C.L. Stern, T.J. Marks and P.N. Nickias, Organometallics 16 (1997) 2503.

    Article  CAS  Google Scholar 

  12. Y.-X. Chen, P.-F. Fu, C.L. Stern and T.J. Marks, Organometallics 16 (1997) 5958.

    Article  CAS  Google Scholar 

  13. M.A. Giardello, M.S. Eisen, C.L. Stern and T.J.Marks, J. Am. Chem. Soc. 117 (1995) 12114.

    Article  CAS  Google Scholar 

  14. M.A. Giardello, M.S. Eisen, C.L. Stern and T.J.Marks, J. Am. Chem. Soc. 115 (1993) 3326.

    Article  CAS  Google Scholar 

  15. Y.-X. Chen, C.L. Stern and T.J. Marks, J. Am. Chem. Soc. 119 (1997) 2582.

    Article  CAS  Google Scholar 

  16. L. Jia, X. Yang, C.L. Stern and T.J. Marks, Organometallics 16 (1997) 842.

    Article  CAS  Google Scholar 

  17. Y.-X. Chen, C.L. Stern, S. Yang and T.J. Marks, J. Am. Chem. Soc. 118 (1996) 12451.

    Article  CAS  Google Scholar 

  18. L. Jia, X. Yang, A. Ishihara and T.J. Marks, Organometallics 14 (1995) 3135.

    Article  CAS  Google Scholar 

  19. X. Yang, C.L. Stern and T.J. Marks, J. Am. Chem. Soc. 116 (1994) 10015.

    Article  CAS  Google Scholar 

  20. L. Jia, X. Yang, C.L. Stern and T.J. Marks, Organometallics 13 (1994) 3755.

    Article  CAS  Google Scholar 

  21. X. Yang, C.L. Stern and T.J. Marks, Angew. Chem. Int. Ed. Engl. 31 (1992) 1375.

    Article  Google Scholar 

  22. X. Yang, C.L. Stern and T.J. Marks, J. Am. Chem. Soc. 113 (1991) 3623.

    Article  CAS  Google Scholar 

  23. X. Yang, C.L. Stern and T.J. Marks, Organometallics 10 (1991) 842.

    Article  Google Scholar 

  24. T. Shiomura, T. Asanuma and N. Inoue, Macromol. Rapid Commun. 17 (1996) 9.

    Article  CAS  Google Scholar 

  25. A.R. Siedel, B. Hanaggi and R.A. Newmark, Macromol. Symp. 89 (1995) 299.

    Google Scholar 

  26. J.C. Vizzini, J.C.W. Chien, N.B. Gaddam and R.A. Newmark, J. Polym. Sci. A: Polym. Chem. 32 (1994) 2049.

    Article  CAS  Google Scholar 

  27. J.C.W. Chien, W. Song and M.D. Rausch, J. Polym. Sci. A: Polym. Chem. 32 (1994) 2387.

    Article  CAS  Google Scholar 

  28. S.S. Reddy and S. Sivaram, Prof. Polym. Sci. 20 (1995) 309.

    Article  CAS  Google Scholar 

  29. C.J. Harlan, S.G. Bott and Z.R. Barron, J. Am. Chem. Soc. 117 (1995) 6465.

    Article  CAS  Google Scholar 

  30. C. Sishta, R. Hathorn and T.J. Marks, J. Am. Chem. Soc. 114 (1992) 1112.

    Article  CAS  Google Scholar 

  31. S. Pasynkiewicz, Polyhedron 9 (1990) 429.

    Article  CAS  Google Scholar 

  32. C.A. Reed, Accts. Chem. Res. 31 (1998) 133 and references therein.

    Article  CAS  Google Scholar 

  33. S.H. Strauss, Chem. Rev. (1993) 927 and references therein.

  34. K. Seppelt, Angew. Chem. Int. Ed. Engl. 32 (1993) 1025 and references therein.

    Article  Google Scholar 

  35. M. Bochmann, Angew. Chem. Int. Ed. Engl. 31 (1992) 1181 and references therein.

    Article  Google Scholar 

  36. C.L. Beswick and T.J. Marks, manuscript in preparation.

  37. P.A. Deck, P.A. Beswick and T.J. Marks, J. Am. Chem. Soc. 120 (1998) 1772.

    Article  CAS  Google Scholar 

  38. P.A. Deck and T.J. Marks, J. Am. Chem. Soc. 117 (1995) 6128.

    Article  CAS  Google Scholar 

  39. R.F. Childs, D.L. Mulholland and A. Nixon, Can. J. Chem. 60 (1982) 801.

    Article  CAS  Google Scholar 

  40. R.F. Childs, D.L. Mulholland and A. Nixon, Can. J. Chem. 60 (1982) 809.

    Article  CAS  Google Scholar 

  41. L. Luo and T.J. Marks, manuscript in preparation.

  42. Y. Sun, R.E.v.H. Spence, W.E. Piers, M. Parvez and G.P.A. Yap, J. Am. Chem. Soc. 119 (1997) 5132.

    Article  CAS  Google Scholar 

  43. A.R. Siedle, R.A. Newmark, W.M. Lamanna and J.N. Schroepfer, Polyhedron 9 (1990) 301.

    Article  CAS  Google Scholar 

  44. L.D. Hansen, E.A. Lewis and D.J. Eatough, in: Analytical Solution Calorimetry, Chemical Analysis Monograph 79, ed. K.J. Grime (Wiley, New York, 1985) ch. 5.

    Google Scholar 

  45. J. Barthel, in: Thermometric Titrations, Chemical Analysis Monograph 45, eds. P.J. Elving and J.D. Winefordner (Wiley, New York, 1975) pp. 47–49, 139–149.

    Google Scholar 

  46. J. Sandstrom, in: Dynamic NMR Spectroscopy(Academic Press, New York, 1982) p. 77.

    Google Scholar 

  47. N.S. Ham and T. Mole, Prog. Nucl. Magn. Reson. Spectrosc. 4 (1989) 91.

    Article  Google Scholar 

  48. J.I. Kaplan and G. Fraenkel, NMR of Chemically Exhanging Systems(Academic Press, New York, 1980) 71.

    Google Scholar 

  49. J.W. Moore and R.G. Pearson, Kinetics and Mechanism, 4th Ed. (Wiley, New York, 1981) and references therein.

    Google Scholar 

  50. H. Maskill, The Physical Basis of Organic Chemistry(Oxford University Press, Oxford, 1985).

    Google Scholar 

  51. N.S. Isaacs, Physical Organic Chemistry, 2nd Ed. (Longman, Exxes, 1995).

  52. N. Herfert and G. Fink, Macromol. Chem. 193 (1992) 773.

    Article  CAS  Google Scholar 

  53. T.-S. Peng, C.H. Winger and J.A. Gladysz, Inorg. Chem. 33 (1994) 2534 and references therein.

    Article  CAS  Google Scholar 

  54. A. Igau and J.A. Gladysz, Organometallics 10 (1991) 2327.

    Article  CAS  Google Scholar 

  55. M.R. Colsman, T.D. Newbound, L.J. Marshall, M.D. Noirot, M.M. Miller, G.P. Wulfsberg, J.S. Frye, O.P. Anderson and S.H. Strauss, J. Am. Chem. Soc. 112 (1990) 2349 and references therein.

    Article  CAS  Google Scholar 

  56. R.J. Kulawiec and T.H. Crabtree, Coord. Chem. Rev. 99 (1990) 89 and references therein.

    Article  CAS  Google Scholar 

  57. NIST Online Database, Chemistry WeBook, 1998.

  58. D.E. Richardson, N.G. Alameddin, M.F. Ryan, T. Hayes, J.R. Eyler and A.R. Siedle, J. Am. Chem. Soc. 119 (1996) 11244 and references therein.

    Article  Google Scholar 

  59. A.L. Castelhano and D. Giller, J. Am. Chem. Soc. 104 (1982) 3655.

    Article  CAS  Google Scholar 

  60. J.A. Connor, M.T. Zafarani-Moattar, J. Bickerton, N.I. Saied, S. Suradi, R. Carson, G.A. Takhin and H.A. Skinner, Organometallics 1 (1982) 1166 and references therein.

    Article  CAS  Google Scholar 

  61. G. Yoneda, S.-M. Lin, L.-P. Wang and D.M. Blake, J. Am. Chem. Soc. 103 (1981) 5768.

    Article  CAS  Google Scholar 

  62. L.E. Schock and T.J. Marks, J. Am. Chem. Soc. 110 (1988) 7701.

    Article  CAS  Google Scholar 

  63. W.A. King, S. Di Bella, A. Gulino, G. Lanza, I. Fragal´a and T.J. Marks, J. Am. Chem. Soc., in press.

  64. J.C. Green, Struct. Bond 43 (1981) 37.

    CAS  Google Scholar 

  65. G. Condorelli, I. Fragal´a, A. Centineo and E. Tondello, J. Organometal. Chem. 87 (1975) 311.

    Article  CAS  Google Scholar 

  66. E. Ciliberto, G. Condorelli, P.J. Fagan, J.M. Manriquez, I. Fragal´a and T.J. Marks, J. Am. Chem. Soc. 103 (1981) 4755.

    Article  CAS  Google Scholar 

  67. G. Lanza, I. Fragal´a and T.J. Marks, J. Am. Chem. Soc. 120 (1998) 8257.

    Article  CAS  Google Scholar 

  68. R. Fusco, L. Longo, F. Masi and F. Garbasi, Macromol. Rapid Commun. 18 (1997) 433.

    Article  CAS  Google Scholar 

  69. R. Fusco, L. Longo, F. Masi and F. Garbasi, Macromolecules 30 (1997) 7673.

    Article  CAS  Google Scholar 

  70. P.-F. Fu, L. Luo, G. Lanza, D.J. Wilson, P.R. Rudolph, I.L. Fragal´a, C.L. Stern and T.J. Marks, submitted for publication.

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  1. Department of Chemistry, Northwestern University, Evanston, IL, 60208-3113, USA

    Lubin Luo & Tobin J. Marks

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Luo, L., Marks, T.J. Ziegler–Natta catalyst activation. Thermodynamic and kinetic aspects of metallocenium ion-pair formation, dissociation, and structural reorganization. Topics in Catalysis 7, 97–106 (1999). https://doi.org/10.1023/A:1019155515306

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