No abstract

Reaction of Si(1,3-tBu2-CsH3)Me3 with MCI 4 (M = Ti, Zr) in toluene or hexane at room temperature affords the new trichloromonociclopentadienyl-type derivatives [M(1,3-tBu2-'qS-CsH3)CI3] (M = Ti (2), Zr (3)]. Treatment of complexes 2 and 3 with appropriate alkylating reagents in hexane gives the 1,3-di(tert-butyl)cyclopentadienyl trialkyl titanium and zirconium complexes [M(1,3-tBu2-r/5-C5H3)R3] [M = Ti, R = CH 3 (4), CH2Ph (5); M = Zr, R = CH 3 (6), CH2Ph (7), CH2CMe2Ph (8)]. Interestingly, when 2 reacts with 3.1 equivalents of LiCH2CMeePh in hexane at room temperature the ring-tert-butyl-metallated complex [Ti(1-tBu-3-CMe2CH2-r/5-CsH3) (CH2CMe2Ph) 2] (9) was isolated in 90% yield. The cationic mono (1,3-di-(tert-butyl)cyclopentadienyl) dibenzyl zirconium species [Zr(1,3-tBu2-@-CsH3)(CH2Ph)2] +, generated in situ by reaction of the tribenzyl complex 7 with B(C6F5) 3 or [CPh3]+[B(C6Fs)4] -reagents, is reported and their dynamic NMR behaviour in CDzCI 2 solutions at low temperatures is studied.