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

Tetrabenzo[a,c,g,i]fluorene (Tbf-H, 4) was deprotonated with n-butyllithium, leading to ionic Tbf-LiL n 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 Cl x Ti(O i Pr) 4-x (x = 1, 3) and chlorotitanium phenoxides {ClTi(OR) 3 (THF)} 2 (R = C 6 H 5 (12), 4-MeC 6 H 4 (13), 4- t BuC 6 H 4 (14)) give a series of η 5 -tetrabenzo[a,c,g,ι]fluorenyltitanium complexes (TbfTiCl 2 (O i Pr) (11) and TbfTi(OR) 3 [R = i Pr (10), C 6 H 5 (15), 4-MeC 6 H 4 (16), 4- t BuC 6 H 4 (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 x mol styrene x h]: 11 (1420) < 17 (3400) < 16 (3740) < 10 (6040) < 15 (6720).