Monocyclopentadienyl titanium complexes supported by functionalized carboxylate ligands

The reaction of [TiCp*Cl3] with [Fe(η5-C5H5)(η5-C5H4COOH)] in the presence of NEt3 yields [TiCp*{(OOC–C5H4)FeCp}3] (1), (Cp = η5-C5H5). The alkyl complex [TiCp*Me3] reacts with [FeCp(η5-C5H4–CH2COOH)] or anthranilic acid rendering the tris-carboxylate titanium complexes [TiCp*{(OOCCH2–C5H4)FeCp}3] (2) and [TiCp*{(OOCC6H4NH2)3] (3), respectively. Complex 3 can be protonated with triflic acid to render [TiCp*{(OOCC6H4NH2)3].HOTf (4). The reaction of [TiCp*Me3] with anthranilic acid in a 1:2 M ratio yields the alkyl carboxylate derivative [TiCp*Me{(OOCC6H4NH2)2] (5). Complex 5 reacts with tBuNC to render the iminoacyl complex [TiCp*(η2-MeCNtBu){(OOCC6H4NH2)2] (6). The reaction of [TiCp*Cl3] with the ferroceneacetic acid, gives [TiCp*Cl2{(OOCCH2–C5H4)FeCp}] (7). The [TiCp*Cl]2(μ–O)[(ΟΟC–C5H4)2Fe] (8) can be obtained by reaction of [TiCp*Cl3] with [Fe(η5-C5H4–COOH)2] in the presence of a base. The molecular structures of 1 and 8 have been established by X-ray diffraction methods.