Chiral C1-symmetric group 4 metallocenes as catalysts for stereoregular α-olefin polymerization. metal, ancillary ligand, and counteranion effects

Michael A. Giardello, Moris S. Eisen, Charlotte L. Stern, Tobin J Marks

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This contribution reports the synthesis and activity as precatalysts for stereoselective propylene polymerization of several chiral non-C2 symmetric zirconocene and hafnocene complexes, (R)- and (S)-M2Si(Me4C5)-(C5H 3R*)MR2 (R = Cl(2) or Me(3)) where R* = (1R,2S,5R)-trans-5-methyl-cis-2-(2-propyl)cyclohexyl ((-)-menthyl; M = Zr, (a) and M = Hf, (b)) and (1S,2S,5R)-trans-5-methyl-cis-2-(2-propyl)cyclohexyl ((+)-neomenthyl; M = Zr (c)). Metallocene dichlorides were prepared from MCl4 and Li2Me2Si(Me4C5)(C5H 3R*) and converted to the corresponding dimethyl complexes with MeLi·LiBr. All complexes were characterized by standard techniques, with absolute configuration established by circular dichroism and X-ray diffraction. For the (R) - R* = (-)-menthyldichloro complex (2a): space group = P212121; a = 9.404(2), b = 9.817(3), c = 28.684(7) Å(-120°C), Z = 4; R(F) = 0.056, AW(F) = 0.061 for 2025 reflections having I > 3σ(I). For the (R) - R* = (-)-menthyldimethyl complex (3a): space group = P21; a = 9.501(3), b = 9.394(3), c = 15.565(3) Å, β= 103.76(2)°(-120°C), Z = 2; R(F) = 0.037, Rw(F) = 0.039 for 1528 reflections having I > 3σ(I). Reaction of either (R)-3a or (R)-3b with B(C6F5)3 in toluene yields two spectroscopically discernible methyl cations. The temperature dependence of the ion-pair equilibrium constant in toluene yields ΔH = -0.7(1) kcal/mol and ΔS = -3.1(1) eu for (R)-3a and ΔH = 0.14(3) kcal/mol and ΔS = -3.1(1) for (R)-3b. "Cationic" propylene polymerization catalysts were generated from 2 + methylalumoxane or 3 + methylalumoxane, B(C6F5)3, Ph3C+B(C6F5)4 -, or HN(nBu3)+B(C6F5) 4-. Polymerization activities, stereoregularities, and polymer molecular weights are strongly dependent on cocatalyst identities and concentrations, suggesting strong, structure-sensitive ion-pairing effects. Polypropylene isotacticities as high as 95% mmmm pentad content are observed, with stereoregularity increasing and polymerization activity falling with decreasing reaction temperature.

Original languageEnglish
Pages (from-to)12114-12129
Number of pages16
JournalJournal of the American Chemical Society
Issue number49
Publication statusPublished - Dec 13 1995


ASJC Scopus subject areas

  • Chemistry(all)

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