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Carbazolyl-Substituted [OSSO]-Type Zirconium(IV) Complex as a Precatalyst for the Oligomerization and Polymerization of α-Olefins

Department of Chemistry, Graduate School of Science and Engineering, Saitama University, 255 Shimo-okubo, Sakura-ku, Saitama 338-8570, Japan
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Catalysts 2019, 9(6), 528; https://doi.org/10.3390/catal9060528
Received: 9 May 2019 / Revised: 1 June 2019 / Accepted: 7 June 2019 / Published: 13 June 2019
(This article belongs to the Special Issue Catalysis in α-Olefin Polymerization/Oligomerization)
The dibenzyl zirconium(IV) complex (4) incorporating with a carbazolyl(Cbz)-substituted [OSSO]-type bis(phenolate) ligand was synthesized. Upon activation with dried modified methylaluminoxane (dMMAO), precatalyst 4 at relatively low catalyst loadings was found to promote the 1,2-regioselective oligomerization of 1-hexene to produce the corresponding vinylidene-ended oligomers with moderate turnover frequencies (TOFs) up to 2080 h−1. The 13C NMR analysis of the resulting oligomers revealed the formation of dimer-enriched oligo(1-hexene)s in 39–62% distributions. The precatalyst 4 with dried methylaluminoxane (dMAO) also exhibited good performance in the polymerization of styrene yielding isotactic polystyrenes ([mm] > 99%) with quite large molecular weights (Mw < 508,100 g mol−1) and relatively high catalytic activity (up to 2810 g mmol(4)−1 h−1). View Full-Text
Keywords: zirconium; oligomerization; polymerization zirconium; oligomerization; polymerization
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Nakata, N.; Nakamura, K.; Nagaoka, S.; Ishii, A. Carbazolyl-Substituted [OSSO]-Type Zirconium(IV) Complex as a Precatalyst for the Oligomerization and Polymerization of α-Olefins. Catalysts 2019, 9, 528.

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