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Volumn 122, Issue 32, 2000, Pages 7750-7767

d0 Metal olefin complexes. Synthesis, structures, and dynamic properties of (C5R5)2Zr(OCMe2CH2CH2CH=CH2)<+ complexes: Models for the elusive (C5R5)2Zr(R)(Olefin)+ intermediates in metallocene-based olefin polymerization catalysis

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; METAL COMPLEX; ZIRCONIUM DERIVATIVE;

EID: 0034674902     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja000989p     Document Type: Article
Times cited : (92)

References (198)
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    • 4] to generate zirconocene species: (a) Chien, J. C. W.; Tsai, W.-M., Rausch, M. D. J. Am. Chem. Soc. 1991, 113, 8570. (b) Ewen, J. A.; Elder, M. J. Eur. Patent Appl. 0,426,637, 1991; Chem. Abstr. 1991, 115, 136988d.
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    • Guram, A.S.1    Swenson, D.C.2    Jordan, R.F.3
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    • Antonelli, D.M.1    Tjaden, E.B.2    Stryker, J.M.3
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    • IV carbonyl complexes see; (a) Guram, A. S.; Swenson, D. C.; Jordan, R. F. J. Am. Chem. Soc. 1992, 114, 8991. (b) Antonelli, D. M.; Tjaden, E. B.; Stryker, J. M. Organometallics 1994, 13, 763. (c) Guo, Z. G.; Swenson, D. C.; Guram, A. S.; Jordan, R. F. Organometallics 1994, 13, 766. (d) Manriquez, J. M.; McAlister, D. R.; Sanner, R. D.; Bercaw, J. E. J. Am. Chem. Soc. 1978, 100, 2716. (e) Manriquez, J. M.; McAlister, D. R.; Sanner, R. D.; Bercaw, J. E. J. Am. Chem. Soc. 1976, 98, 6733. (f) Marsella, J. A.; Curtis, J. C: Bercaw, J. E.; Caulton, K. G. J. Am. Chem. Soc. 1980, 102, 7244. (g) Howard, W. A.; Trnka, T. M.; Parkin, G. Organometallics 1995, 14, 4037. (h) Brakemeyer, T.; Erker, G.; Fröhlich, R. Organometallics 1997, 16, 531.
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    • Guo, Z.G.1    Swenson, D.C.2    Guram, A.S.3    Jordan, R.F.4
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    • IV carbonyl complexes see; (a) Guram, A. S.; Swenson, D. C.; Jordan, R. F. J. Am. Chem. Soc. 1992, 114, 8991. (b) Antonelli, D. M.; Tjaden, E. B.; Stryker, J. M. Organometallics 1994, 13, 763. (c) Guo, Z. G.; Swenson, D. C.; Guram, A. S.; Jordan, R. F. Organometallics 1994, 13, 766. (d) Manriquez, J. M.; McAlister, D. R.; Sanner, R. D.; Bercaw, J. E. J. Am. Chem. Soc. 1978, 100, 2716. (e) Manriquez, J. M.; McAlister, D. R.; Sanner, R. D.; Bercaw, J. E. J. Am. Chem. Soc. 1976, 98, 6733. (f) Marsella, J. A.; Curtis, J. C: Bercaw, J. E.; Caulton, K. G. J. Am. Chem. Soc. 1980, 102, 7244. (g) Howard, W. A.; Trnka, T. M.; Parkin, G. Organometallics 1995, 14, 4037. (h) Brakemeyer, T.; Erker, G.; Fröhlich, R. Organometallics 1997, 16, 531.
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    • Manriquez, J.M.1    McAlister, D.R.2    Sanner, R.D.3    Bercaw, J.E.4
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    • (1980) J. Am. Chem. Soc. , vol.102 , pp. 7244
    • Marsella, J.A.1    Curtis, J.C.2    Bercaw, J.E.3    Caulton, K.G.4
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    • IV carbonyl complexes see; (a) Guram, A. S.; Swenson, D. C.; Jordan, R. F. J. Am. Chem. Soc. 1992, 114, 8991. (b) Antonelli, D. M.; Tjaden, E. B.; Stryker, J. M. Organometallics 1994, 13, 763. (c) Guo, Z. G.; Swenson, D. C.; Guram, A. S.; Jordan, R. F. Organometallics 1994, 13, 766. (d) Manriquez, J. M.; McAlister, D. R.; Sanner, R. D.; Bercaw, J. E. J. Am. Chem. Soc. 1978, 100, 2716. (e) Manriquez, J. M.; McAlister, D. R.; Sanner, R. D.; Bercaw, J. E. J. Am. Chem. Soc. 1976, 98, 6733. (f) Marsella, J. A.; Curtis, J. C: Bercaw, J. E.; Caulton, K. G. J. Am. Chem. Soc. 1980, 102, 7244. (g) Howard, W. A.; Trnka, T. M.; Parkin, G. Organometallics 1995, 14, 4037. (h) Brakemeyer, T.; Erker, G.; Fröhlich, R. Organometallics 1997, 16, 531.
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    • Howard, W.A.1    Trnka, T.M.2    Parkin, G.3
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    • IV carbonyl complexes see; (a) Guram, A. S.; Swenson, D. C.; Jordan, R. F. J. Am. Chem. Soc. 1992, 114, 8991. (b) Antonelli, D. M.; Tjaden, E. B.; Stryker, J. M. Organometallics 1994, 13, 763. (c) Guo, Z. G.; Swenson, D. C.; Guram, A. S.; Jordan, R. F. Organometallics 1994, 13, 766. (d) Manriquez, J. M.; McAlister, D. R.; Sanner, R. D.; Bercaw, J. E. J. Am. Chem. Soc. 1978, 100, 2716. (e) Manriquez, J. M.; McAlister, D. R.; Sanner, R. D.; Bercaw, J. E. J. Am. Chem. Soc. 1976, 98, 6733. (f) Marsella, J. A.; Curtis, J. C: Bercaw, J. E.; Caulton, K. G. J. Am. Chem. Soc. 1980, 102, 7244. (g) Howard, W. A.; Trnka, T. M.; Parkin, G. Organometallics 1995, 14, 4037. (h) Brakemeyer, T.; Erker, G.; Fröhlich, R. Organometallics 1997, 16, 531.
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    • -1.
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    • note
    • int of the coordinated olefin.
  • 104
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    • note
    • 2 resonances than for the Cp resonances (Δδ = 0.115 and 0.035 respectively at -80°C), which affords greater precision in the exchange rate determination. Simulation of the Cp resonances in the range -80 to -50°C led to similar activation parameters.
  • 109
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    • note
    • 2 solvent, so the influence of solvent properties could not be investigated conveniently.
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    • 2 groups are diastereotopic due to their proximity to the chiral rac-(EBI)Zr unit.
  • 111
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    • note
    • anti resonances (Δδ = 0.04), which results in greater precision in the exchange rate determination.
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    • Brooks/Cole: Monterey, CA
    • ⊄ values below -10 eu. However, activation entropies are difficult to determine precisely and must be interpreted carefully because of possible contributions from solvent reorganization, especially for polar solvents and charged metal complexes. See: (a) Atwood, J. D. Inorganic and Organometallic Reaction Mechanisms; Brooks/Cole: Monterey, CA, 1985; p 17. (b) Jordan, R. B. Reaction Mechanisms of Inorganic and Organometallic Systems; Oxford University: New York, 1991; pp 56-57.
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    • ⊄ values below -10 eu. However, activation entropies are difficult to determine precisely and must be interpreted carefully because of possible contributions from solvent reorganization, especially for polar solvents and charged metal complexes. See: (a) Atwood, J. D. Inorganic and Organometallic Reaction Mechanisms; Brooks/Cole: Monterey, CA, 1985; p 17. (b) Jordan, R. B. Reaction Mechanisms of Inorganic and Organometallic Systems; Oxford University: New York, 1991; pp 56-57.
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    • Jordan, R.B.1
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    • (a) The ionization energies of chlorobenzene (11.4 eV) and dichloromethane (11.35 eV) are similar. See: Debies, T. P.; Rabalais, J. W. J. Electron Spectrosc. 1972, 1, 355. Werner, A. S.; Tsai, B. P.; Baer, T. J. Chem. Phys. 1974, 60, 3650.
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    • note
    • cis will become sharp only above ca. 130 °C (see Figure 3).
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