Preparation and characterization of Cp-functionalized cycloheptatrienyl–cyclopentadienyl titanium sandwich complexes (troticenes)

Cp-functionalized monotroticenes [(η7-C7H7)Ti(η5-C5H4E)] (2, E = Ph2SiCl; 3, E = tBu2SnCl; 12, E = I) and bitroticenes [(η7-C7H7)Ti(η5-C5H4)]2E′ (5, E′ = PPh; 6, E′ = BN(SiMe3)2; 7, E′ = Cp2Ti) were prepared by salt elimination metathesis between the monolithiated troticene [(η7-C7H7)Ti(η5-C5H4Li)]·pmdta (1b) (pmdta = N,N′,N′,N″,N″-pentamethyldiethylene-triamine) and the appropriate electrophile. The troticenyl-substituted zirconocene monochloride [(η7-C7H7)Ti(η5-C5H4ZrClCp*2)] (Cp* = η5-C5Me5) (8) and hafnocene ethoxide [(η7-C7H7)Ti{η5-C5H4Hf(OEt)Cp2}] (Cp = η5-C5H5) (11), and the heterobimetallic μ-oxo complexes [(η7-C7H7)Ti(η5-C5H4MCp2)]2O (9, M = Zr; 10, M = Hf) were obtained instead of the expected zircona- and hafna[1]troticenophanes by reaction of the dilithiated troticene [(η7-C7H6Li)Ti(η5-C5H4Li)]·pmdta (1a) with [Cp2MCl2] (M = Zr, Hf) or [Cp*2ZrCl2] in stoichiometric amounts. These compounds were characterized by single crystal X-ray diffraction analyses and, in the case of 2, 3, 5–7, 9, 10 and 12, also by elemental analyses and 1H, 13C and 119Sn NMR spectroscopy. Exposure of the troticenyl organotin chloride 3 to moisture resulted in its partial hydrolysis and formation of the organostannoxane-bridged bitroticene 4, while palladium-catalyzed Negishi C–C cross-coupling reaction between the troticenylzinc chloride [(η7-C7H7)Ti(η5-C5H4ZnCl)] (13) and the iodotroticene 12 or iodobenzene (PhI) led to the fulvalene complexes [(η7-C7H7)Ti(η5-C5H4)]2 (14) and [(η7-C7H7)Ti(η5-C5H4Ph)] (15). Compound 4 displays an unsymmetrical structure with the troticenyl fragments cis with respect to the Sn–O–Sn core, whereas compound 14 is centrosymmetrically trans oriented.