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Volumn 122, Issue 28, 2000, Pages 6686-6700

Mechanistic studies of Pd(II)-α-diimine-catalyzed olefin polymerizations

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; METHANE; PALLADIUM; POLYETHYLENE;

EID: 0034686736     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja000893v     Document Type: Article
Times cited : (565)

References (88)
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    • For additional references, see: (a) Johnson, L. K.; Killian, C. M. In Metallocene-Based Polyolefins: Preparation, Properties, and Technology; Scheirs, J., Kaminsky, W., Eds.; Wiley: West Sussex, 2000; p 233. (b) Ittel, S. D. In Metalorganic Catalysts for Synthesis and Polymerization; Kaminsky, W., Ed.; Springer-Verlag: Heidelberg, 1999; p 616.
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    • Exceptions for poly(α-olefins) include: (a) Rieger, B.; Mu, X.; Mallin, D. T.; Rausch, M. D.; Chien, J. C. W. Macromolecules 1990, 23, 3559-3568. (b) Soga, K.; Shiono, R.; Takemura, S.; Kaminsky, W. Makromol. Chem. Rapid Commun. 1987, 8, 305-310. (c) Spalek, W., Antberg, M.; Aulbach, M.; Bachmann, B.; Dolle, V.; Haftka, S.; Kuber, F.; Rohrmann, J.; Winter, A. In Ziegler Catalysts; Fink, G., Mülhaupt, R., Brintzinger, H. H., Eds.; Springer: Berlin, 1995; p 83.
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    • Spalek, W.1    Antberg, M.2    Aulbach, M.3    Bachmann, B.4    Dolle, V.5    Haftka, S.6    Kuber, F.7    Rohrmann, J.8    Winter, A.9
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    • A similar observation was reported for a square planar N-alkyl α-diimine complex of nickel in which intramolecular C-H activation of a ligand methyl group occurs to give a five-membered metallacycle: tom Dieck, H.; Svoboda, M. Chem. Ber. 1976, 109, 1657-1664.
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    • We describe here a discrete olefin-hydride intermediate; however, β-H transfer may occur through a concerted process with an olefin-hydride-like transition state, as suggested by Ziegler et al.: (a) Deng, L.; Margl, P.; Ziegler, T. J. Am. Chem. Soc. 1997, 119, 1094-1100 (b) Deng, L.; Woo, T. K.; Cavallo, L.; Margl, P. M.; Ziegler, T. J. Am. Chem. Soc. 1997, 119, 6177-6186.
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    • We describe here a discrete olefin-hydride intermediate; however, β-H transfer may occur through a concerted process with an olefin-hydride- like transition state, as suggested by Ziegler et al.: (a) Deng, L.; Margl, P.; Ziegler, T. J. Am. Chem. Soc. 1997, 119, 1094-1100 (b) Deng, L.; Woo, T. K.; Cavallo, L.; Margl, P. M.; Ziegler, T. J. Am. Chem. Soc. 1997, 119, 6177-6186.
    • (1997) J. Am. Chem. Soc. , vol.119 , pp. 6177-6186
    • Deng, L.1    Woo, T.K.2    Cavallo, L.3    Margl, P.M.4    Ziegler, T.5
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    • For previous studies of alkyl isomerization in unhindered Pd systems, see: (a) Reger, D. L.; Garza, D. G.; Baxter, J. C. Organometallics 1990, 9, 873-874 (b) Reger, D. L.; Garza, D. G.; Lebioda, L. Organometallics 1991, 10, 902-906 (c) Reger, D. L.; Garza, D. G.; Lebioda, L. Organometallics 1992, 11, 4285-4292.
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    • Reger, D.L.1    Garza, D.G.2    Baxter, J.C.3
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    • For previous studies of alkyl isomerization in unhindered Pd systems, see: (a) Reger, D. L.; Garza, D. G.; Baxter, J. C. Organometallics 1990, 9, 873-874 (b) Reger, D. L.; Garza, D. G.; Lebioda, L. Organometallics 1991, 10, 902-906 (c) Reger, D. L.; Garza, D. G.; Lebioda, L. Organometallics 1992, 11, 4285-4292.
    • (1991) Organometallics , vol.10 , pp. 902-906
    • Reger, D.L.1    Garza, D.G.2    Lebioda, L.3
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    • For previous studies of alkyl isomerization in unhindered Pd systems, see: (a) Reger, D. L.; Garza, D. G.; Baxter, J. C. Organometallics 1990, 9, 873-874 (b) Reger, D. L.; Garza, D. G.; Lebioda, L. Organometallics 1991, 10, 902-906 (c) Reger, D. L.; Garza, D. G.; Lebioda, L. Organometallics 1992, 11, 4285-4292.
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    • note
    • 3-Br can result in explosions. This material is commercially available from Boulder Scientific.
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    • note
    • 2O in the sample. The correct chemical shift is δ 16.7 (9 peaks, J = 1.5 Hz, IH).
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    • Technical Report No. ORNL-5138; Oak Ridge National Laboratory: Oak Radge, TN, 1976
    • Johnson, C. K. Technical Report No. ORNL-5138; Oak Ridge National Laboratory: Oak Radge, TN, 1976.
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