Beyond the Active Site. Cp*ZrMe3/Sulfated Alumina-Catalyzed Olefin Polymerization Tacticity via Catalyst⋅⋅⋅Surface Ion-Pairing

Jialong Zhang, Alexander H. Mason, Yang Wang, Alessandro Motta, Takeshi Kobayashi, Marek Pruski, Yanshan Gao*, Tobin J. Marks

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


Surface-bound organometallic molecules have recently enabled the development of single-site heterogeneous catalysts, advancing the atomic scale understanding and diversity of heterogeneous catalysis. Here we report that supporting Cp*ZrMe3 (Cat1) on acidic sulfated-alumina (AlS) affords the surface catalyst Cat1/AlS, which was characterized by multi-dimensional solid-state NMR spectroscopies, and is active in ethylene homo- and copolymerizations, as well as propylene and 1-hexene homopolymerizations. In contrast to propylene (or 1-hexene) polymerization by homogeneous Cp*ZrMe2+ B(C6F5)4 which yields atactic polyolefins, Cat1/AlS promotes remarkable isotacticity with mmmm >95 %. Complementary DFT analysis argues that the restrictive local Cat1/AlS C1-symmetry favors activation and enchainment at the propylene re enantioface, promoting isotactic polymerization via a “back-skip-like” mechanism.

Original languageEnglish (US)
Pages (from-to)2564-2569
Number of pages6
Issue number11
StatePublished - Jun 8 2021


  • Zirconocene
  • isotactic polypropylene
  • olefin polymerization
  • solid-state NMR
  • surface organometallics

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry


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