Amido- and imido-ethylpyridine titanium complexes. Crystal structure of {Ti[NCH2CH2py]Cl2(THF)}2

Abstract Compounds of general formula N(R 1 )(R 2 )CH 2 CH 2 py (py=C 5 H 4 N; R 1 =R 2 =SiMe 3 , 1a ; R 1 =H, R 2 =Si t BuMe 2 , 1b ; R 1 =SiMe 3 , R 2 =Si t BuMe 2 , 1c ; R 1 =SiMe 3 , R 2 =Ph, 5 ) were synthesised. They readily reacted with TiCl 4 to afford the corresponding amidoaminotrichlorides {Ti[N(R 2 )(CH 2 CH 2 py)]Cl 3 } (R 2 =SiMe 3 , 2a ; R 2 =Si t BuMe 2 , 2b ; R 2 =Ph, 6 ). The related imido derivatives {Ti[N(CH 2 CH 2 py)]Cl 2 } n ( 3b ) and {Ti[N(CH 2 CH 2 py)](L)Cl 2 } 2 (L=THF, 3c ; PMe 3 , 3d ) were isolated upon heating and reaction with L, respectively. Reaction of 6 with THF afforded the corresponding adduct, {Ti[N(Ph)(CH 2 CH 2 py)](THF)Cl 3 } ( 7 ). Compound 3b reacted with LiNMe 2 to give asymmetrical {Ti 2 [N(CH 2 CH 2 py)][N(CH 2 CH 2 py)]′Cl 4 } ( 4a ). Compound {CpTi[N(CH 2 CH 2 py)]Cl} n ( 4b ), was formed when 3b reacted with NaCp. Analogous studies with 2a and 6 led to Cp 2 TiCl 2 . {Cp 2 Ti 2 [μ-N(Ph)]Cl 2 } ( 8 ) was isolated as the product of CpTiCl 3 and Na[N(Ph)CH 2 CH 2 py]. The molecular structure of 3c was determined by X-ray single crystal diffraction.