Abstract
Two diiminobis(phenolate) zirconium complexes [C6H10-{NCH-(3,5-tBu2C6H2-2-O)-κO}2]ZrX2 [X = CH2Ph (1), Cl (3)] have been synthesized and characterized by NMR solution spectroscopy. Complex 1 was found conformationally stable and isolated in the octahedral C2 symmetric form. When exposed to the light in hydrocarbon solution, 1 readily undergoes to 1,2 benzyl migration converting the diiminobis(phenolate) ligand in the corresponding benzylamidoiminobis(phenolate). Complex 3 is more thermally stable and found in slow equilibrium between the cis-α and cis-β forms with the former largely prevalent (9:1 molar ratio). The rate of interconversion between the two diastereoisomers was estimated in 3.6 × 10-1 s-1 by NMR exchange spectroscopy (EXSY). 1 and 3 are active ethylene polymerization catalysts after reaction with MAO or [CPh3][B(C6F5)4]/Al-iBu3. The polydispersity index of polyethylene produced by 1 is about 2, suggesting the presence of a single active species and that the symmetry of the precatalyst is ret...
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