Zirconium-alkyl isomerizations in zirconocene-catalyzed olefin polymerization: A density functional study

Organometallics

Volumn 16, Issue 18, 1997, Pages 3889-3894

  Prosenc, Marc Heinrich ^a   Brintzinger, Hans Herbert ^a  

^a UNIVERSITY OF KONSTANZ   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001094242     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om970227b     Document Type: Article

References (64)

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45. Zr-C(1) and Zr-C(2) distances of 228 pm found for this species are close to those observed in various zirconocene olefin complexes (228-238 pm). Buchwald, S. L.; Lum, R. T.; Dewan, J. C. J. Am. Chem. Soc. 1986, 108, 7441. Buchwald, S. L.; Watson, W. T.; Huffman, J. C. J. Am. Chem. Soc. 1987, 109, 2544. Alt, H. G.; Benner, C. E.; Thewalt, U.; Rausch, M. D. J. Organomet. Chem. 1988, C83, 356. Binger, P.; Müller, P.; Benn, R.; Rufinska, R.; Gabor, B.; Krüger, C.; Bete, P. Chem. Ber. 1989, 122, 1035. Takahashi, T.; Murakami, M.; Kunishinga, M.; Saburi, M.; Uchida, Y.; Kozawa, K.; Uchida, T.; Swanson, D. R.; Negishi, E. Chem. Lett. 1989, 761. Goddard, R.; Binger, P.; Hall, S. R.; Müller, P. Acta Crystallogr., Sect. C 1990, 46, 998.
46. Zr-C(1) and Zr-C(2) distances of 228 pm found for this species are close to those observed in various zirconocene olefin complexes (228-238 pm). Buchwald, S. L.; Lum, R. T.; Dewan, J. C. J. Am. Chem. Soc. 1986, 108, 7441. Buchwald, S. L.; Watson, W. T.; Huffman, J. C. J. Am. Chem. Soc. 1987, 109, 2544. Alt, H. G.; Benner, C. E.; Thewalt, U.; Rausch, M. D. J. Organomet. Chem. 1988, C83, 356. Binger, P.; Müller, P.; Benn, R.; Rufinska, R.; Gabor, B.; Krüger, C.; Bete, P. Chem. Ber. 1989, 122, 1035. Takahashi, T.; Murakami, M.; Kunishinga, M.; Saburi, M.; Uchida, Y.; Kozawa, K.; Uchida, T.; Swanson, D. R.; Negishi, E. Chem. Lett. 1989, 761. Goddard, R.; Binger, P.; Hall, S. R.; Müller, P. Acta Crystallogr., Sect. C 1990, 46, 998.
47. Zr-C(1) and Zr-C(2) distances of 228 pm found for this species are close to those observed in various zirconocene olefin complexes (228-238 pm). Buchwald, S. L.; Lum, R. T.; Dewan, J. C. J. Am. Chem. Soc. 1986, 108, 7441. Buchwald, S. L.; Watson, W. T.; Huffman, J. C. J. Am. Chem. Soc. 1987, 109, 2544. Alt, H. G.; Benner, C. E.; Thewalt, U.; Rausch, M. D. J. Organomet. Chem. 1988, C83, 356. Binger, P.; Müller, P.; Benn, R.; Rufinska, R.; Gabor, B.; Krüger, C.; Bete, P. Chem. Ber. 1989, 122, 1035. Takahashi, T.; Murakami, M.; Kunishinga, M.; Saburi, M.; Uchida, Y.; Kozawa, K.; Uchida, T.; Swanson, D. R.; Negishi, E. Chem. Lett. 1989, 761. Goddard, R.; Binger, P.; Hall, S. R.; Müller, P. Acta Crystallogr., Sect. C 1990, 46, 998.
48. Zr-C(1) and Zr-C(2) distances of 228 pm found for this species are close to those observed in various zirconocene olefin complexes (228-238 pm). Buchwald, S. L.; Lum, R. T.; Dewan, J. C. J. Am. Chem. Soc. 1986, 108, 7441. Buchwald, S. L.; Watson, W. T.; Huffman, J. C. J. Am. Chem. Soc. 1987, 109, 2544. Alt, H. G.; Benner, C. E.; Thewalt, U.; Rausch, M. D. J. Organomet. Chem. 1988, C83, 356. Binger, P.; Müller, P.; Benn, R.; Rufinska, R.; Gabor, B.; Krüger, C.; Bete, P. Chem. Ber. 1989, 122, 1035. Takahashi, T.; Murakami, M.; Kunishinga, M.; Saburi, M.; Uchida, Y.; Kozawa, K.; Uchida, T.; Swanson, D. R.; Negishi, E. Chem. Lett. 1989, 761. Goddard, R.; Binger, P.; Hall, S. R.; Müller, P. Acta Crystallogr., Sect. C 1990, 46, 998.
49. Zr-C(1) and Zr-C(2) distances of 228 pm found for this species are close to those observed in various zirconocene olefin complexes (228-238 pm). Buchwald, S. L.; Lum, R. T.; Dewan, J. C. J. Am. Chem. Soc. 1986, 108, 7441. Buchwald, S. L.; Watson, W. T.; Huffman, J. C. J. Am. Chem. Soc. 1987, 109, 2544. Alt, H. G.; Benner, C. E.; Thewalt, U.; Rausch, M. D. J. Organomet. Chem. 1988, C83, 356. Binger, P.; Müller, P.; Benn, R.; Rufinska, R.; Gabor, B.; Krüger, C.; Bete, P. Chem. Ber. 1989, 122, 1035. Takahashi, T.; Murakami, M.; Kunishinga, M.; Saburi, M.; Uchida, Y.; Kozawa, K.; Uchida, T.; Swanson, D. R.; Negishi, E. Chem. Lett. 1989, 761. Goddard, R.; Binger, P.; Hall, S. R.; Müller, P. Acta Crystallogr., Sect. C 1990, 46, 998.
50. Zr-C(1) and Zr-C(2) distances of 228 pm found for this species are close to those observed in various zirconocene olefin complexes (228-238 pm). Buchwald, S. L.; Lum, R. T.; Dewan, J. C. J. Am. Chem. Soc. 1986, 108, 7441. Buchwald, S. L.; Watson, W. T.; Huffman, J. C. J. Am. Chem. Soc. 1987, 109, 2544. Alt, H. G.; Benner, C. E.; Thewalt, U.; Rausch, M. D. J. Organomet. Chem. 1988, C83, 356. Binger, P.; Müller, P.; Benn, R.; Rufinska, R.; Gabor, B.; Krüger, C.; Bete, P. Chem. Ber. 1989, 122, 1035. Takahashi, T.; Murakami, M.; Kunishinga, M.; Saburi, M.; Uchida, Y.; Kozawa, K.; Uchida, T.; Swanson, D. R.; Negishi, E. Chem. Lett. 1989, 761. Goddard, R.; Binger, P.; Hall, S. R.; Müller, P. Acta Crystallogr., Sect. C 1990, 46, 998.
51. + cation. Ajith Perera, S. A., Bartlett, R. J.; Schleyer, P. v. R. J. Am. Chem. Soc. 1995, 117, 8476.
52. 2O: Wu, Z.; Jordan, R. F.; Petersen, J. L. J. Am. Chem. Soc. 1995, 117, 5867.
53. The olefin in complex E-4 has a bonding energy of 98 kJ/mol relative to the dissociated species.
54. 5 ring ligands.
55. Prosenc, M. H.; Brintzinger, H. H. Manuscript in preparation.
56. Busico, V.; Cipullo, R.; Corradini, P. Makromol. Chem., Rapid Commun. 1992, 13, 15, 21; 1993, 14, 97. Jüngling, S.; Mülhaupt, R.; Stehling, U.; Brintzinger, H. H.; Fischer, D.; Langhauser, F. J. Polym. Sci.: Part A: Polym. Chem. 1995, 33, 1305.
57. Busico, V.; Cipullo, R.; Corradini, P. Makromol. Chem., Rapid Commun. 1992, 13, 15, 21; 1993, 14, 97. Jüngling, S.; Mülhaupt, R.; Stehling, U.; Brintzinger, H. H.; Fischer, D.; Langhauser, F. J. Polym. Sci.: Part A: Polym. Chem. 1995, 33, 1305.
58. Busico, V.; Cipullo, R.; Corradini, P. Makromol. Chem., Rapid Commun. 1992, 13, 15, 21; 1993, 14, 97. Jüngling, S.; Mülhaupt, R.; Stehling, U.; Brintzinger, H. H.; Fischer, D.; Langhauser, F. J. Polym. Sci.: Part A: Polym. Chem. 1995, 33, 1305.
59. 2Sc-propyl.
60. The energy of the doubly β-agostic cation B-5 is calculated to be 5 kJ/mol lower than that of a singly β-agostic cation analogous to P-5.
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62. Not considered here is a rotation of the two olefin termini of the isobutene ligand relative to each other.
63. s-symmetric geometry with the H atoms at C(2) and C(3) in contact with the Zr center and the C(1)-C(4) olefin plane in the zirconocene bisector plane. For the activation energy of this rearrange-ment we find a value of 80 kj/mol.
64. 5-ring centroids in B-1 and B-2.