Unusual Cationic Trinuclear Nickel Clusters Incorporating Oxazolines or N,N,N′,N′-Tetramethylethylene-1,2-diamine: Applications in Olefin Polymerization
2011-10-17T00:00:00Z (GMT) by
The synthesis and characterization of two rare examples of the nickel(II)-containing trinuclear clusters of the general formula μ3-halido-μ3-hydroxotris(μ-halido)tris(L) trinickel(II) halide [halide = Cl (2), Br (3); L = 4,4-dimethyl-2-(o-anilinyl)-2-oxazoline] are described. These materials are compared and contrasted to the “parent” chloride salt (1) of this series (L = N,N,N′,N′-tetramethylethylene-1,2-diamine and halide = Cl) and its congeners; 2 and 3 represent the first oxazoline-containing clusters of this structural class. Both 1 and 2 are shown to be active catalysts for the polymerization of olefins (styrene, methyl methacrylate, etc.) using a stoichiometric equivalent of methylaluminoxane as the copromoter, a situation that gives good yields of syndiotactic rich polymers. Density functional theory (B3LYP/6-31G*/LANL2DZ) is employed to hypothesize the likely origin of the activity demonstrated by these compounds.