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

Abstract

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).