Synthesis and imido-group exchange reactions of tert-butylimidotitanium complexes

Abstract
Treatment of TiCl 4 with Bu t NH 2 (6 equivalents) followed by addition of bpy (2 equivalents, 4-tert-butylpyridine) or pyridine (py) (2 or 4 equivalents) afforded the five- or six-co-ordinate tert-butylimido complexes [Ti(NBu t )Cl 2 (bpy) 2 ] or [Ti(NBu t )Cl 2 (py) n ] (n = 2 or 3*) respectively in good yields. Reaction of [Ti(NBu t )Cl 2 (py) 3 ] with RNH 2 gave the corresponding arylimido derivatives [Ti(NR)Cl 2 (py) 3 ] (R = Ph,* C 6 H 4 Me-4,* C 6 H 4 NO 2 -4,* C 6 H 3 Me 2 -2,6 or C 6 H 3 Pr i 2 -2,6). Addition of tmen or pmdien to [Ti(NBu t )Cl 2 (py) n ] (n = 2 or 3 respectively) gave the corresponding bi- or tri-dentate amine complexes, [Ti(NBu t )Cl 2 (tmen)] or [Ti(NBu t )Cl 2 (pmdien)]* (tmen = Me 2 NCH 2 CH 2 NMe 2 , pmdien = N,N,N′,N ″,N″ -pentamethyldiethylenetriamine). Complexes labelled * have been crystallographically characterised.

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