Catalytically Active N-Acylamidine–Zirconium Complexes: Synthesis, Structures, and Application in Ethylene Polymerization

Abstract

Three novel N-acylamidines 1a–c with varying steric bulk and substitution patterns were synthesized and thoroughly characterized by X-ray diffraction. Compounds 1a and 1b, which contain two additional binding sites located at two pyridine substituents, were treated with equimolar amounts of cyclopentadienylzirconium(IV) trichloride at room temperature. The X-ray data of the resulting coordination compounds 7a and 7b indicate the formation of five-membered metallacycles with one of the pyridine nitrogen atoms and the carbonyl oxygen atom acting as binding sites. For the complexation of ligand 1c, a different route was chosen: 1c was first deprotonated to yield the polymeric potassium compound 8 with a very complex substitution pattern based on O , N, and aromatic interactions with the potassium ions. Transmetalation of 8 with cyclopentadienylzirconium(IV) trichloride gave amidinate complex 9, which is dimeric in the solid state but exists in solution in equilibrium with monomeric species. After addition of...