Density functional study of ethylene-norbornene copolymerization via metallocene and constrained-geometry catalysts

Organometallics

Volumn 23, Issue 13, 2004, Pages 3319-3326

  Kim, Eung Gun ^a,b   Klein, Michael L ^a  

^a UNIVERSITY OF PENNSYLVANIA   (United States)

^b GEORGIA INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CONSTRAINED GEOMETRY CATALYSTS (CGC); DENSITY FUNCTION THEORY (DFT); STERIC INTERACTION; STRAIN ENERGY;

ACTIVATION ENERGY; CATALYSTS; COMPUTATIONAL GEOMETRY; COPOLYMERIZATION; ENERGY GAP; ETHYLENE; FREE ENERGY; OPTIMIZATION; PHASE TRANSITIONS; PROBABILITY DENSITY FUNCTION; RATE CONSTANTS; REACTION KINETICS; STRUCTURAL ANALYSIS;

ORGANOMETALLICS;

EID: 3042781130     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om034136s     Document Type: Article

References (37)

1. Kaminsky, W.; Bark, A.; Arndt, M. Makromol. Chem., Macromol. Symp. 1991, 47, 83.
2. (a) Ruchatz, D.; Fink, G. Macromolecules 1998, 31, 4669.
3. (b) Macromolecules 1998, 31, 4674.
4. (c) Macromolecules 1998, 31, 4681.
5. (d) Macromolecules 1998, 31, 4684.
6. (a) Thorshaug, K.; Mendichi, R.; Boggioni, L.; Tritto, I.; Trinkle, S.; Friedrich, C.; Mülhaupt, R. Macromolecules 2002, 35, 2903.
7. (b) Tritto, I.; Boggioni, L.; Jansen, J. C.; Thorshaug, K.; Sacchi, M. C.; Ferro, D. R. Macromolecules 2002, 35, 616.
8. (c) Provasoli, A.; Ferro, D. R.; Tritto, I.; Boggioni, L. Macromolecules 1999, 32, 6697.
9. (d) Tritto, I.; Marestin, C.; Boggioni, L.; Zetta, L.; Provasoli, A.; Ferro, D. R. Macromolecules 2000, 33, 8931.
10. (e) Tritto, I.; Marestin, C.; Boggioni, L.; Sacchi, M. C.; Brintzinger, H.-H.; Ferro, D. R. Macromolecules 2001, 34, 5770.
11. (a) Bergström, C. H.; Väänänen, T. L. J.; Seppälä, J. V. J. Appl. Polym. Sci. 1997, 63, 1071.
12. (b) Bergström, C. H.; Sperlich, B. R.; Ruotoistenmäki, J.; Seppälä, J. V. J. Polym. Sci. A: Polym. Chem. 1998, 36, 1633.
13. Park, S. Y.; Choi, K. Y.; Song, K. H.; Jeong, B. G. Macromolecules 2003, 36, 4216.
14. Mod. Plast. 1995, 72, 137.
15. Arndt, M.; Engehausen, R.; Kaminsky, W.; Zoumis, K. J. Mol. Catal. A: Chem. 1995, 101, 171.
16. Cossee, P. J. Catal. 1964, 3, 80.
17. Brookhart, M.; Green, M. L. H. J. Organomet. Chem. 1983, 250, 395.
18. (a) Kawamura-Kuribayashi, H.; Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1992, 114, 8687.
19. (b) Yoshida, T.; Koga, N.; Morokuma, K. Organometallics 1996, 15, 766.
20. (a) Cavallo, L.; Guerra, G. Macromolecules 1996, 29, 2729.
21. (b) Iarlori, S.; Buda, F.; Meier, R. J.; van Doremaele, G. H. J. Mol. Phys. 1996, 87, 801.
22. (a) Woo, T. K.; Fan, L.; Ziegler, T. Organometallics 1994, 13, 2252.
23. (b) Fan, L.; Harrison, D.; Woo, T. K.; Ziegler, T. Organometallics 1995, 14, 2018.
24. (c) Lohrenz, J. C. W.; Woo, T. K.; Ziegler, T. J. Am. Chem. Soc. 1995, 117, 12793.
25. (d) Lohrenz, J. C. W.; Woo, T. K.; Fan, L.; Ziegler, T. J. Organomet. Chem. 1995, 497, 91.
26. (e) Margl, P.; Lohrenz, J. C. W.; Ziegler, T.; Blöchl, P. E. J. Am. Chem. Soc. 1996, 118, 4434.
27. +, for instance, the metal charge was 0.617 (0.833 with LANL2DZ) and the metal-Cp distance was 2.217 (2.233) Å. However, the conclusions of the study remained unaffected, indicative of the minor role played by the spectator ligands in the copolymerization reaction.
28. Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299.
29. Dunning, T. H., Jr.; Hay, P. J. In Modern Theoretical Chemistry; Schaefer, H. F., III, Ed.; Plenum: New York, 1976; Vol. 3, pp 1-28.
30. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98; Gaussian, Inc.: Pittsburgh, PA, 1998.
31. Atkins, P. W. Physical Chemistry, 2nd ed.; Oxford University Press: Oxford, U.K., 1982.
32. McQuarrie, D. A. Statistical Mechanics; Harper Collins: New York, 1976.
33. The released strain energy was estimated by comparing the hydrogenation reactions of norbornene and ethylene. An eclipsed conformation was used for ethane because the corresponding bond in norbornane is nonrotatable. The same procedure was also used for bicyclooctene.
34. Polypropylene and Other Polyolefins; van der Ven, S., Ed.; Eisevier: Amsterdam, The Netherlands, 1990; p 413.
35. Sykes, P. A Guidebook to Mechanism in Organic Chemistry, 6th ed.; Longman Scientific & Technical: Essex, U.K., 1986; pp 259-260.
36. The exclusive exo insertion has been reported also in late-transition-metal catalysis. For a recent review on this topic, see: Goodall, B. L. In Late Transition Metal Polymerization Catalysis; Rieger, B., Baugh, L. S., Kacker, S., Striegler, S., Eds.; Wiley-VCH: Weinheim, Germany, 2003; pp 101-154.
37. Arndt, M. Dissertation, Universität Hamburg; Hamburg, Germany, 1993.