REACTIONS OF ORGANOTITANOXANE FLUORIDES WITH AIR3 (R = ME, ET, CH2PH) AND ME3SICL : X-RAY CRYSTAL STRUCTURES OF C5ME5TI(MU -O)4F(MU -F)ALME33, C5ME5TI (MU -O)4F3(MU -F)AL(CH2PH)3, C5ME5TI(MU -O)ET4, AND (C5ME5)4TI4O5X2 (X = CL AND F)

A new pentamethylcyclopentadienyl titanoxane fluoride (C5Me5)4Ti4O5F2 (1b) has been synthesized from (C5Me5)4Ti4O5Cl2 using the fluorinating reagent Me3SnF. The fluorination of organotitanoxane chlorides proceeds via a proposed intermediate similar to the four-membered ring Ti(μ-Cl)(μ-F)Sn and the bridged Ti(μ-F)ClSnMe3 species. The reactions of 1b and [C5Me5Ti(μ-O)F]4 with AlR3 (R = Me, Et, CH2Ph) afforded the thermally unstable adducts [C5Me5Ti(μ-O)]4F4-n[(μ-F)AlR3]n (n = 1−4), which proceed with selective exchange of fluorine atoms for alkyl groups to give an eight-membered alkylated ring compound [C5Me5Ti(μ-O)R]4. The reactions of 1b and [C5Me5Ti(μ-O)F]4 with Me3SiCl result in exchange of fluorine for chlorine atoms. Moreover, using an excess of Me3SiCl leads to a novel oxygen−chlorine exchange reaction to give C5Me5TiCl3. The crystal structures of complexes (C5Me5)4Ti4O5X2 (X = Cl (1a), F (1b)), [C5Me5Ti(μ-O)]4F[(μ-F)AlMe3]3 (2b), [C5Me5Ti(μ-O)]4F3[(μ-F)Al(CH2Ph)3] (3a), and [C5Me5Ti(μ-O)Et]4 (4) hav...