Tetrabenzo[<i>a,c,g,i</i>]fluorenyllithium and η⁵-Tetrabenzo[<i>a,c,g,i</i>]fluorenyltitanium Complexes

Tetrabenzo[a,c,g,i]fluorene (Tbf-H, 4) was deprotonated with n-butyllithium, leading to ionic Tbf-LiLn complexes 5 and 6, consisting of well-separated cations (Li(THF)4 (5), Li(DME)3 (6)) and Tbf anions. Subsequent reactions with chlorotitanium alkoxides ClxTi(OiPr)4-x (x = 1, 3) and chlorotitanium phenoxides {ClTi(OR)3(THF)}2 (R = C6H5 (12), 4-MeC6H4 (13), 4-tBuC6H4 (14)) give a series of η5-tetrabenzo[a,c,g,i]fluorenyltitanium complexes (TbfTiCl2(OiPr) (11) and TbfTi(OR)3 [R = iPr (10), C6H5 (15), 4-MeC6H4 (16), 4-tBuC6H4 (17)]), which were characterized by NMR, MS, and IR measurements and X-ray crystallography. Additionally, the compounds' properties regarding the syndiospecific polymerization of styrene when activated with MAO were explored. The activities increase in the following order [kg sPS/(mol Ti × mol styrene × h]: 11 (1420) < 17 (3400) < 16 (3740) < 10 (6040) < 15 (6720).