Studies on the active species in olefin polymerisation generated from phenoxo-amido titanium "chiral-at-metal" compounds

Article abstract of DOI:10.1016/j.jorganchem.2011.02.011

Treatment of RHN-CH₂-(3,5-tBu₂C₆H ₂-2-OH) (R = C₆H₅ 1a, p-MeC₆H ₄ 1b, Cy 1c; Cy = cyclohexyl) with 1 equiv of TiCpCl₃ (Cp = η⁵-C₅Me₅) in the presence of 2.5 equiv of NEt₃ in pentane or hexane at room temperature gives the monocyclopentadienyl phenoxo-amido monochloro complexes [TiCp{RN-CH ₂-(3,5-tBu₂C₆H₂-2-O)}Cl] (R = C ₆H₅ 2, p-MeC₆H₄ 4, Cy 5). In a more polar solvent the phenoxo-amino complex [TiCp{(C₆H ₅)(H)N-CH₂-(3,5-tBu₂C₆H ₂-2-O)}Cl₂] (3) is obtained from the reaction with 1a. The reaction of TiCpCl₃ with tBu(H)N-CH₂-(3,5-tBu ₂C₆H₂-2-OH) (1d) affords the complex [TiCp{tBu(H)N-CH₂-(3,5-tBu₂C₆H ₂-2-O)}Cl₂] (6) in which no coordination of the amino group to the metal centre is observed as a consequence of the high steric requirements of the amino substituent in the phenol-amine. All the reported compounds were characterised by the usual analytical and spectroscopic methods and the molecular structures of 2 and 5 were determined by X-ray diffraction analysis from suitable single crystals. Studies of catalytic activity for ethylene or propylene polymerisation using boron or aluminium reagents as cocatalysts were performed under different conditions. In general the trends observed for the phenoxo-amido precatalysts with the aluminium reagent as cocatalyst in the α-olefin polymerisation reactions might suggest a catalyst decomposition process through ligand abstraction by sMAO. The activity found for ethylene or propylene polymerisation when B(C₆F ₅)₃ or [CPh₃][B(C₆F ₅)₄] are used as cocatalysts is related to the strength of the cation-anion interactions.