CONTROLLED HYDROLYSIS OF TRIPODAL TITANIUM AMIDO HALIDES - THE INFLUENCE OF THE LIGAND PERIPHERY UPON THE BASICITY OF THE AMIDO-N FUNCTIONS

Hydrolysis of the tripodal amidotitanium halides H3CC(CH(2)NSiMe(3))(3 )TiX (X = Cl: 1a; Br: 1b) in the presence of Et(3)N affords the linear mu-oxo-bridged complex [H3CC(CH(2)NSiMe(3))(3)Ti](2) (mu-O) (3) which was characterized by X-ray crystallography. Treatment of H3CC(CH2NiPr )(3)TiX (X = Cl: 2a; Br: 2b), obtained in low yields, under the same c onditions only leads to decomplexation of the amido Ligand. Under cond itions of very slow exposure to H2O the primary addition product of wa ter across two Ti-N bonds in 2a could be isolated and was characterize d as [H3CC(CH2NiPr)(2)CH(2)NHiPr]Ti(mu-Cl)](2)(mu-O) (4), the crystal structure analysis establishing a triply bridging central Ti(mu-O)(mu- Cl)(2)Ti unit. Deprotonation with two molar equivalents of nBuLi and s ubsequent LiCl elimination afforded the mu-oxo complex [H3CC(CH2NiPr)( 3)Ti](2)(mu-O) (5).