Copolymerization of Ethylene with Cyclohexene (CHE) Catalyzed byNonbridgedHalf-Titanocenes Containing Aryloxo Ligand: Notable Effect of Both Cyclopentadienyl and Anionic Donor Ligand for Efficient CHE Incorporation

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Abstract
Cyclohexene (CHE) has been incorporated into the polymer chain in ethylene/CHE copolymerization by nonbridged half-titanocenes containing aryloxo ligands of the type, Cp‘TiCl2(O-2,6-iPr2C6H3), in the presence of methylaluminoxane (MAO) cocatalyst. The effect of the substituent in the cyclopentadienyl fragment was found to be very important for CHE incorporation; both the tert-BuCp (3) and 1,2,4-Me3Cp analogues (4) showed efficient CHE incorporation, whereas a negligible amount of CHE incorporation was observed by both the indenyl (1) and the Cp* analogue (2) under the same conditions. Cp-ketimide analogue, CpTiCl2(NCtBu2) (5), zirconocene-like Cp2ZrCl2 (6), and linked half-titanocene-like [Me2Si(C5Me4)(NtBu)]TiCl2 (7) did not show any CHE incorporation under the same conditions; unique characteristics for using this type of catalyst precursor for the present copolymerization have thus been emphasized.

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