The Kinetic Stability of Cationic Benzyl Titanium Complexes that Contain a Linked Amido-Cyclopentadienyl Ligand: The Influence of the Amido-Substituent on the Ethylene Polymerization Activity of “Constrained Geometry Catalysts”

Cationic benzyl titanium complexes [Ti(η⁵: η¹-C₅Me₄SiMe₂NR')-(CH₂Ph)]⁺ were cleanly formed by the reaction of the dibenzyl titanium complexes [Ti(η⁵: η¹-C₅Me₄SiMe₂NR')(CH₂Ph)₂] with B(C₆F₅)₃ and [Ph₃C][B(C₆F₅)₄] in bromobenzene. NMR spectroscopic studies suggest that the benzyl titanium cations contain a fluxional η²-coordinated benzyl ligand. Kinetic analysis showed that the benzyl titanium cations decompose according to first-order kinetics and that the amido substituents R' (R' = Me, ⁱPr, ^tBu) in the linked amido-cyclopentadienyl ligand influence the lability of these benzyl titanium cations. The order of the kinetic stability of the benzyl titanium cations was found for both anions to follow the order R' = Me > ⁱPr > ^tBu. The benzyl titanium cations generated with [Ph₃C][B(C₆F₅)₄] were found to undergo faster decomposition than those generated with B(C₆F₅)₃. The ethylene polymerization activity order for both systems was found to be the reverse: R' = ^tBu > ⁱPr > Me. The decomposition of the benzyl titanium cations was suggested to occur via C—H activation with concomitant toluene elimination.