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*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

166 Scopus citations


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)-Me2Si(Me4C5)-(C5H3R*)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)(C5H3R*) 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 = F212121; a = 9.404(2), b = 9.817(3), c = 28.684(7) Å(-120 °C), Z = 4; R(F) — 0.056, Rw(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 AS = -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 (US)
Pages (from-to)12114-12129
Number of pages16
JournalJournal of the American Chemical Society
Issue number49
StatePublished - Jan 1 1995

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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