Synthese und Strukturen von Monoalkylamiden und -imiden des Titans

A new method for the preparation o f monoalkylamides o f composition Cp'TiCl2N H R is reported. Me3SnNHR (R = /Bu la , CH/Pr-, lb ) reacts with Cp'TiCl3 with elimination o f M e3SnCl to yield Cp'TiCLNHR (2) (2a: Cp' = C5H 5, R = /Bu, 2b: Cp' = Me3SiC5H4, R = t Bu, 2c: Cp' = (M e3Si)?C5H3, R = /Bu, 2d: Cp' = Me4C5H, R = /Bu, 2e: Cp' = Me5C5, R = t Bu, 2f: Cp' = C5H 5, R = CH/Pr2, 2g: Cp' = M e3SiC5H4, R = CH/Pr2, 2h: Cp' = (M e3Si)2C5H3, R = CH/Pr2, 2i: Cp' = Me4C5H, R = CH/Pr2, 2j: Cp' = Me5C5, R = CH/Pr2). Compounds 2 a 2 j are stable and eliminate HC1 only in the presence o f a strong base to form (C5H 5TiClN/Bu)2 (3a) or (M e3SiC5H4TiC lN /Bu)2 (3b) from 2a and 2b, respectively. In 3a the chlorine atoms are substituted by N H /Bu groups in boiling THF by means o f LiNH/Bu to give (C5H5TiN H /BuN /Bu)2 (4). The reactions o f 2e and 2b with LiN(SiM e3)2Et20 in the presence o f pyridine yield Me5C5TiClN/Bu • Py (5 a) (Py = pyridine) and Me3SiC5H4T iC lN /B u P y (5 b), respectively. Compounds 2e and 5 a have been characterized by X-ray crystal structural analysis.