Vanadium Complexes Possessing N2O2S2-Based Ligands:  Highly Active Procatalysts for the Homopolymerization of Ethylene and Copolymerization of Ethylene/1-hexene

Homden, Damien M.; Redshaw, Carl; Hughes, David L.

Abstract

The family of ligands containing an N2O2S2 core, namely, 1,2-di(3-Me-5-t-Bu-salicylaldimino-o-phenylthio)ethane (H 2L1), 1,3-di(3-Me-5-t-Bu-salicylaldimino-o-phenylthio) propane (H2L2), 1,4-di(3-Me-5-t-Bu-salicylaldimino-o- phenylthio)-butane (H2L3), and 1,2-di(3-Me-5-t-Bu- salicylaldamino-o-phenylthio)ethane (H2L4), have been prepared and complexed with a variety of vanadium chlorides and alkoxides to afford complexes of the form [V(X)L1] (X = O (1), Np-tol (2), Cl (3)), [V(O)(L2,3)] (L2 (4), L3 (5)), and [V(L4)] (6). Crystal structure determinations of H2L 1 and H2L4 show the molecule to be centrosymmetric about the bridging ethane moiety, with structural determination of 1 and 3 revealing isostructural monomeric complexes in which the ligand chelates in such a way as to afford pseudo-octahedral coordination at the vanadium center. Prolonged reaction of H2L1 with [V(Np-tol)(OEt)3] led, via oxidative cleavage of the C-S bond, to the bimetallic complex [V2L1(3-Me,5-t-Bu-salicylaldimino-o- phenylthiolate)2] [VL′] (7), as characterized by single-crystal X-ray crystallography. 7 was also isolated from the reaction of H 2L4 and [VO-(On-Pr)3]. The ability of 1-7 to catalyze the homopolymerization of ethylene and the copolymerization of ethylene/1-hexene in the presence of dimethylaluminum chloride (DMAC) has been assessed: screening reveals that for ethylene homopolymerization 1-7 are all highly active (>1000 g/mmol·h·bar), with the highest activity (ca. 11 000 g/mmol·h·bar) observed using catalyst 3; the use of trimethyl aluminum (TMA) or methylaluminoxane (MAO) as the cocatalyst led only to poorly active systems producing negligible polymer. Analysis of the polyethylene produced showed high molecular weight linear polymers with narrow polydispersities. For ethylene/1-hexene copolymerization, activities as high as 1 190 g/mmol·h·bar were achieved (4); analysis of the copolymer indicated an incorporation of 1-hexene in the range of 5-13%. © 2007 American Chemical Society.

Citation

Homden, D. M., Redshaw, C., & Hughes, D. L. (2007). Vanadium Complexes Possessing N2O2S2-Based Ligands:  Highly Active Procatalysts for the Homopolymerization of Ethylene and Copolymerization of Ethylene/1-hexene. Inorganic chemistry, 46(25), 10827-10839. https://doi.org/10.1021/ic701461b

• Journal Article Type: Article
• Publication Date: Dec 10, 2007
• Deposit Date: Jun 8, 2022
• Journal: Inorganic Chemistry
• Print ISSN: 0020-1669
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 46
• Issue: 25
• Pages: 10827-10839
• DOI: https://doi.org/10.1021/ic701461b
• Public URL: https://hull-repository.worktribe.com/output/3622609