Heteroatom-substituted constrained-geometry complexes. Dramatic substituent effect on catalyst efficiency and polymer molecular weight

Organometallics

Volumn 20, Issue 13, 2001, Pages 2663-2665

  Klosin, Jerzy ^a   Kruper Jr , William J ^a   Nickias, Peter N ^a   Roof, Gordon R ^a   De Waele, Phillip ^a   Abboud, Khalil A ^b  

^a DOW CHEMICAL COMPANY   (United States)

^b University of Florida ^*  (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYST ACTIVITY; COMPLEXATION; COPOLYMERIZATION; COPOLYMERS; MOLECULAR WEIGHT; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; SINGLE CRYSTALS; SYNTHESIS (CHEMICAL); X RAY DIFFRACTION ANALYSIS;

CONSTRAINED-GEOMETRY COMPLEXES; ELEMENTAL ANALYSIS; SUBSTITUENT EFFECT;

ORGANOMETALLICS;

EID: 0035948489     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om010016d     Document Type: Article

References (39)

1. Albright, L. F. Polym. News 1997, 22, 281-284.
2. (a) Gladysz, J. A. Chem. Rev. 2000, 100, 1167-1682.
3. (b) Marks, T. J.; Stevens, J. C. Top. Catal. 1999, 7, 1-208.
4. (c) Jordan, R. F. J. Mol. Catal. 1998, 128, 1-337.
5. (d) Piers, W. E. Chem. Eur. J. 1998, 4, 13-18.
6. (e) Metallocenes; Togni, A., Halterman, R. L., Eds.; Wiley-VCH: Weinheim, Germany, 1998.
7. (f) Kaminsky, W.; Arndt, M. Adv. Polym. Sci. 1997, 127, 144-187.
8. (g) Bochmann, M. J. Chem. Soc., Dalton Trans. 1996, 255-270.
9. (h) Brintzinger, H.-H.; Fischer, D.; Mülhaupt, R.; Rieger, B.; Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143-1170.
10. (a) Stevens, J. C. Stud. Surf. Sci. Catal. 1994, 89, 277-284.
11. (b) Stevens, J. C.; Timmers, F. J.; Wilson, D. R.; Schmidt, G. F.; Nickias, P. N.; Rosen, R. K.; Knight, G. W.; Lai, S. Eur. Patent Appl. EP-416-815-A2, 1991.
12. For early work on constrained-geometry complexes see: (a) Shapiro, P. J.; Cotter, W. D.; Schaefer, W. P.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1994, 116, 4623-4640.
13. (b) Piers, W. E.; Shapiro, P. J.; Bunel, E. E.; Bercaw, J. E. Synlett 1990, 2, 74-84.
14. (c) Shapiro, P. J.; Bunel, E. E.; Schaefer, W. P.; Bercaw, J. E. Organometallics 1990, 9, 867-869.
15. (d) Canich, J. M. U.S. Patent 5,026,798, 1991.
16. (e) Okuda, J. Chem. Ber. 1990, 123, 1649-1651.
17. For reviews of constrained-geometry complexes see: (a) McKnight, A. L.; Waymouth, R. M. Chem. Rev. 1998, 98, 2587-2598.
18. (b) Okuda, J.; Eberle, T. In Metallocenes; Togni, A., Halterman, R. L., Eds.; Wiley-VCH: Weinheim, Germany, 1998; pp 415-453.
19. Pine, S. H. Organic Chemistry; McGraw-Hill: Englewood Cliffs, NJ, 1987; pp 609-638.
20. Stahl, K.; Boche, G.; Massa, W. J. J. Organomet. Chem. 1984, 277, 113-125.
21. Communicated in part: (a) Klosin, J.; Kruper, J. W.; Nickias, P. N.; Patton, J. T.; Abboud, K. A. Book of Abstracts, 217th National Meeting of the American Chemical Society, Anaheim, CA, 1999; American Chemical Society: Washington, DC, 1999; INOR-694.
22. (b) Klosin, J.; Kruper, W. J.; Nickias, P. N.; Patton, J. T.; Wilson, D. R. WO 980672, 1998.
23. (c) Klosin, J.; Kruper, W. J.; Nickias, P. N.; Patton, J. T.; Wilson, D. R. WO 9806728, 1998.
24. 2SiTi: C, 64.60; H, 8.78; N, 7.17. Found: C, 64.30; H, 8.95; N, 6.72.
25. Finch, W. C.; Anslyn, E. V.; Grubbs, R. H. J. Am. Chem. Soc. 1988, 110, 2406-2413.
26. -1, F(000) = 904, 15 220 reflections collected, 4955 independent reflections, GOF = 1.024, R1 = 0.0296 (I > 2δ (I)), wR2 = 0.0788 (all data).
27. (a) Yang, X.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1991, 113, 3623-3625.
28. (b) Ewen, J. A.; Elder, M. J. Eur. Patent Appl. 0,427,697, 1991.
29. (c) Massey, A. G.; Park, A. J. J. Organomet. Chem. 1964, 2, 245-250.
30. Interaction of the heteroatom substutuent with an activator (MAO) was proposed as a possible explanation of very poor activity of alkoxy-substitutued titanium trichloride in syndiotactic polystyrene polymerization: Foster, P.; Rausch, M. D.; Chien, J. C. W. J. Organomet. Chem., 1997, 527, 71-74.
31. Yang, X.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1994, 116, 10015-10031.
32. Details of this chemistry will be described in future publications.
33. 19F NMR.
34. The 2-pyrrolidino-substituted complex (direct analogue of 4b) was also prepared and was found to exhibit polymerization characteristics very similar to those of 2b.
35. The polymerization activity of complexes 1b-3b and 5b at 0.05 μmol loading was also studied and was not enhanced comparedto that of higher catalyst loading. The amount of 4b was kept below 0.1 μmol to maintain a polymerization exotherm within 10 °C.
36. (a) Barsties, E.; Schaible, S.; Prosenc, M.-H.; Rief; U.; Roll, W.; Weyand, O.; Dorer, B.; Brintzinger, H. H. J. Organomet. Chem., 1996, 520, 63-68.
37. (b) Luttikhedde, H. J. G.; Leino, R. P.; Wilén, C.-E.; Näsman, J. H.; Ahlgren, M. J.; Pakkanen, T. A. Organometallics 1996, 15, 3092-3094.
38. (a) Patton, J. T.; Klosin, J.; Kruper, W. J.; Abboud, K. A. Book of Abstracts, 216th National Meeting of the American Chemical Society, Boston, MA, 1998; American Chemical Society: Washington, DC, 1998; INOR 94.
39. (b) Klosin, J.; Kruper, J. W.; Patton, J. T.; Abboud, K. A. Manuscript in preparation.