o-Phenylene-bridged Cp/sulfonamido titanium complexes for ethylene/1-octene copolymerization

摘要

The Suzuki-coupling reaction of 2-(dihydroxyboryl)-3,4-dimethyl-2-cyclopenten-1-one (1) and 2-(dihydroxyboryl)-3-methyl-2-cyclopenten-1-one (2) with 2- bromoaniline derivatives affords cyclopentenone compounds (3-8) from which cyclopentadiene compounds, 4,6-R'(2)-2-(2,5-Me2C5H3)C6H2NH2 (9-11) and 4,6-R'(2)-2-(2,3,5-Me3C5H2)C6H2NH2 (12-14) are prepared. After sulfonation of the -NH2 group with p-TsCl, metallation is carried out by successive addition of Ti(NMe2)(4) and Me2SiCl2 affording o-phenylene-bridged Cp/sulfonamido titanium dichloride complexes, [4,6-R'(2)-2-(2,5-Me2C5H2)C6H2NSO2C6H4CH3)]TiCl2 (R'=H, 21; R'=Me, 22; R'= F, 23) and [4,6-R'(2)-2-(2,3,5-Me3C5H)C6H2NSO2C6H4CH3)]TiCl2(R'= H, 24; R'=Me, 25; R'=F, 26). The molecular structures of 24 and [2-(2,5-Me2C5H2)C6H4NSO2C6H4CH3)] Ti(NMe2)(2) (27) are determined by X-ray crystallography. The Cp(centroid)-Ti-N angle in 24 is smaller (100.90.) than that observed for the CGC (constrained-geometry catalyst), [Me2Si(eta(5)-Me4Cp)(NtBu)]TiCl2 (107.6.) indicating a more "constrained feature" in 24 than in the CGC. Complex 24 shows the highest activity among the newly prepared complexes in ethylene/1-octene copolymerization but it is slightly inferior to the CGC in terms of activity, comonomer-incorporation ability, and molecular weight of the obtained polymers.