ABSTRACT: Two diiminobis(phenolate) zirconium complexes [C6H10-{NdCH-(3,5-tBu2C6H2-2-O)-O}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-R and cis-â 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 retained during polymerization. The catalyst is stable over 3 h, and the polymerization activity linearly increases with time. Copolymers of ethylene with propylene or 1-hexene were synthesized, and the 13C NMR analysis of their microstructure suggested the highly regioregular 1,2 insertion of the 1-olefin and the inability of the ligand environment to express stereochemical control during monomer insertion.
Olefin polymerization promoted by a stereorigid bridged diimonobis(phenolate)zirconium complex
CUOMO, Cinzia;STRIANESE, MARIA;GRASSI, Alfonso
2004-01-01
Abstract
ABSTRACT: Two diiminobis(phenolate) zirconium complexes [C6H10-{NdCH-(3,5-tBu2C6H2-2-O)-O}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-R and cis-â 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 retained during polymerization. The catalyst is stable over 3 h, and the polymerization activity linearly increases with time. Copolymers of ethylene with propylene or 1-hexene were synthesized, and the 13C NMR analysis of their microstructure suggested the highly regioregular 1,2 insertion of the 1-olefin and the inability of the ligand environment to express stereochemical control during monomer insertion.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
