Eight different zirconium phenoxyimine complexes were synthesized, characterized and tested as catalysts for ethylene polymerization. The phenoxyimine compounds were prepared by condensation of substituted salicylaldehydes with aliphatic and aromatic amines, the substituted salicylaldehydes from ortho substituted phenols and paraformaldehyde. The introduction of iodo substituents was achieved e...

We already reported that an intramolecular benzylation of the imino moiety of bidentate iminopyrrolyl ligands afforded an amido-pyrrolyl complexes 1 and they exhibited better catalytic activity for ethylene polymerization compared to the corresponding bis(iminopyrrolyl) dichloro complexes of zirconium. In this contribution, we prepared amido-pyrrolyl complexes of zirconium (3a-d) and hafnium (4...

In general, ethylene/1,3-butadiene copolymerizations provides copolymers possessing both pendant vinyls and vinylenes as olefinic moieties. We, at MCI, studied the substituent effects of C2-symmetric zirconocene complexes, rac-[Me2Si(Indenyl’)2]ZrCl2 (Indenyl’ = generic substituted indenyl), after activation on the ratio of the pendant vinyls and vinylenes of the resultant copolymers. Complexes...

A series of 8 new complexes of titanium and zirconium with diamido ligands bearing an ethylene and propylene bridge between the two amido groups were synthesized and tested for ethylene polymerization. Titanium complexes bearing an ethylene bridge between the two amido groups showed higher activities than the derivatives with a propylene bridge. In the case of the zirconium complexes, the p...

Treatment of tetrakis(diethylamido)zirconium(IV); [Zr(NEt2)4] with a series of β-ketoimines ({[RHN]C(CH3)=C(H)C(CH3)=O} where R is a functionalized side-chain; 4-(2-methoxyethylamino)pent-3-en-2-one, Hmeap; 4-(3-methoxypropylamino)pent-3-en-2-one, Hmpap; 4-(2-(dimethylamino)ethylamino)pent-3-en-2-one, Hdeap; 4-(3-(dimethylamino)propylamino)pent-3-en-2-one, Hdpap) leads to an amine substitution ...

A series of parasubstituted tetraphenylporphyrin zirconium(IV) salicylate complexes (SA/5-SSAZr(IV)RTPP, R = p-H, p-CH3, p-NO2, p-Cl, SA = salicylate, and 5-SSA = 5-sulfosalicylate) have been synthesized, and the spectral properties of free base porphyrins, their corresponding metallated, and axially ligated zirconium(IV) porphyrin compounds were compared with each other. A detailed analysis of...

Reaction of a zinc/zirconium heterobimetallic complex with 1,5-cyclooctadiene (1,5-COD) results in slow isomerization to 1,3-cyclooctadiene (1,3-COD), along with the formation of a new complex that includes a cyclooctyne ligand bridging two metal centers. While analogous magnesium/zirconium and aluminum/zirconium heterobimetallic complexes are competent for the catalytic isomerization of 1,5-CO...

The syntheses of a series of tris(amidate) mono(amido) titanium and zirconium complexes are reported. The binding motif of the amidate ligand has been determined to depend on the size of the metal centre for these sterically demanding N,O-chelating ligands; the larger zirconium metal centre supports three κ(2)-(N,O) bound amidate ligands while the titanium analogue has one ligand bound in a κ(1...

 A series of seven new complexes of zirconium and hafnium with bulky ω-aryloxyalkyl substituted indenyl ligands were synthesized and characterized by NMR spectroscopy and elemental analysis. These complexes were activated with methylaluminoxane and tested for homogeneous ethylene polymerization. The zirconium catalysts showed higher activities than their hafnium an...