Polymerizable group 4 ansa-cyclopentadienyl-amido catalysts for the copolymerization of ethylene with 1-octene

The trinuclear zirconium imido complex [{LZr(NMe)}] (2, L = CMeCHCHN) was synthesized by amine elimination between Zr(NMe) and endo-olefinic isomers of (tetramethylcyclopentadienyl)ethanamine (LH) (1). To study the fundamental reactivity of the trizirconium system, reactions of 2 with primary amines were examined. Selective incorporations of the primary amines were observed, depending on steric and electronic natures of the amine substrates. The amine-incorporated complexes [(LZrNHR)(LHZrNHR)(LHZr)(μ-NHR)(μ-NR)] (3, R = Pr, Et), [(LZrNHR)(LHZr)(μ-NR)] (4, R = Pr, i-Bu), [(LZr)(LZrNMe)(μ-NR)] (5, R = neo-Pen), and [(LZr)(LZrNHAr)(LHZr)(μ-NAr)] (6, Ar = Ph, CH-4-Br, CH-4-OMe) were structurally characterized by NMR and XRD analysis and showed several coordination modes of the substrate nitrogen ligands: i.e., terminal amides, bridging amides, and bridging imides but not terminal imides. Thermolysis of a mixture of 3 and 4 led to C-H bond activation, giving rise to the zirconaaziridines [{LZr(η-NCHR)}(LZr)(LHZr)(μ-NHCHR)] (12, R = Et, Me). Complex 2 proved to be a competent precatalyst in the hydroamination of the aminoalkynes (HNCHCRCHC≡CR) (13, R = H, R = Bu, Ph, t-Bu; 14, R = Me, R = Et, Ph). Stoichiometric or semicatalytic reactions of 2 and the aminoalkynes were studied to explore the reactivity of in situ formed Zr species.

show abstract

Polymerizable group 4 ansa-cyclopentadienyl-amido catalysts for the copolymerization of ethylene with 1-octene

Cited by 3 publications

References 32 publications

Biaryl Group 4 Metal Complexes as Non‐Metallocene Catalysts for Polyethylene with Long Chain Branching

Biaryl Group 4 Metal Complexes as Non‐Metallocene Catalysts for Polyethylene with Long Chain Branching

Zirconium Complexes

Selective Incorporation of Primary Amines into a Trizirconium Imido System and Catalyic Cyclization of Aminoalkynes

Contact Info

Product

Resources

About