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

Dalton Transactions Pub Date: 2006-07-03 DOI: 10.1039/B605345A

Abstract

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(η5-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.

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