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Dinickel Bisphenoxyiminato Complexes for the Polymerization of Ethylene and α-Olefins
Organometallics (2012)
  • Madalyn R. Radlauer, California Institute of Technology
  • Michael W. Day, California Institute of Technology
  • Theodor Agapie, California Institute of Technology
Dinuclear nickel phenoxyiminato olefin polymerization catalysts based on rigid p-terphenyl frameworks are reported. Permethylation of the central arene of the terphenyl unit and oxygen substitution of the peripheral rings ortho to the aryl–aryl linkages blocks rotation around these linkages, allowing atropisomers of the ligand to be isolated. The corresponding syn and anti dinickel complexes (25-s and 25-a) were synthesized and characterized by single-crystal X-ray diffraction. These frameworks limit the relative movement of the metal centers, restricting the metal–metal distance. Kinetics studies of isomerization of a ligand precursor (7-a) allowed the calculation of the activation parameters for the isomerization process (ΔH = 28.0 ± 0.4 kcal × mol–1 and ΔS = −12.3 ± 0.4 cal mol–1 K–1). The reported nickel complexes are active for ethylene polymerization (TOF up to 3700 (mol C2H4) (mol Ni)−1 h–1) and ethylene/α-olefin copolymerization. Only methyl branches are observed in the polymerization of ethylene, while α-olefins are incorporated without apparent chain walking. These catalysts are active in the presence of polar additives and in neat tetrahydrofuran. The syn and anti isomers differ in polymerization activity, polymer branching, and polymer molecular weight. For comparison, a series of mononuclear nickel complexes (2627-s27-a2830) was prepared and studied. The effects of structure and catalyst nuclearity on reactivity are discussed.
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Madalyn R. Radlauer, Michael W. Day and Theodor Agapie. "Dinickel Bisphenoxyiminato Complexes for the Polymerization of Ethylene and α-Olefins" Organometallics Vol. 31 Iss. 6 (2012) p. 2231 - 2243 ISSN: 0276-7333
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