Reactivity of chlorodimethylsilyl-η5-cyclopentadienyltrichlorotitanium with nitrogen based donors. X-ray molecular structure of [Ti{η5-C5H4SiMe2[η1-N(2,6-Me2C6H3)]}Cl2]

Abstract

This paper reports the reactivity of [Ti(η5-C5H4SiMe2Cl)Cl3], 1 towards nitrogen based donor reagents. Complex 1 reacts with lithium benzamidinato Li[PhC(NSiMe3)2] to afford [Ti(η5-C5H4SiMe2Cl){PhC(NSiMe3)2}Cl2] 2 and with lithium amide LiNMe2 to produce [Ti(η5-C5H4SiMe2NMe2)(NMe2)3] 3. The latter compound was converted into the dihalide derivatives [Ti(η5-C5H4SiMe2NMe2)(NMe2)X2] [X=Cl (4) and Br (5)] by reaction with SiMe3X (X=Cl or Br, respectively). The constrained geometry derivatives [Ti{η5-C5H4SiMe2(η1-NR)}Cl2] (R=C6H56, 2,6-Me2C6H37 and 2-Me-6-iPr-C6H38) have been synthesized by treatment of 1 with the corresponding primary aryl amines H2NR. Complex 7 was readily converted into the dialkyl and diamido compounds [Ti{η5-C5H4SiMe2[η1-N(C6H3Me2)]}X2] (X=Me (9), CH2Ph (10), CH2SiMe3 (11) or NMe2 (13)) by metathesis using Grignard or organolithium reagents and into the monoalkyl derivative [Ti{η5-C5H4SiMe2[η1-N(C6H3Me2)]}MeCl] (12) by reaction with AlMe3. The molecular structure of complex 7 [Ti{(η5-C5H4SiMe2[η1-N(2,6-Me2C6H3)]}Cl2] was established by X-ray crystallography.