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 H 3 CC(CH 2 NSiMe 3 ) 3 TiX (X = Cl: 1a ; Br: 1b ) in the presence of Et 3 N affords the linear μ‐oxo‐bridged complex [H 3 CC(CH 2 NSiMe 3 ) 3 Ti] 2 (μ‐O) ( 3 ) which was characterized by X‐ray crystallography. Treatment of H 3 CC(CH 2 N i Pr) 3 TiX (X = Cl: 2a ; Br: 2b ), obtained in low yields, under the same conditions only leads to decomplexation of the amido ligand. Under conditions of very slow exposure to H 2 O the primary addition product of water across two Ti–N bonds in 2a could be isolated and was characterized as [H 3 CC(CH 2 ‐i(μ‐Cl)] 2 (μ‐O) ( 4 ), the crystal structure analysis establishing a triply bridging central Ti(μ‐O)(μ‐Cl) 2 Ti unit. Deprotonation with two molar equivalents of n BuLi and subsequent LiCl elimination afforded the μ‐oxo complex [H 3 CC(CH 2 N i Pr) 3 Ti] 2 (μ‐O) ( 5 ).