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

This paper reports the reactivity of [Ti(eta(5)-C5H4SiMe2Cl)Cl-3] towards nitrogen based donor reagents. Complex 1 reacts with lithium benzamidinato Li[PhC(NSiMe3)(2)] to afford [Ti(eta(5)-C5H4SiMe2Cl){PhC(NSiMe3)(2)}Cl-2] 2 and with lithium amide LiNMe2 to produce [Ti(eta(5) -C5H4SiMe2NMe2)(NMe2)(3)] 3. The latter compound was converted into the dihalide derivatives [Ti(eta(5)-C5H4SiMe2NMe2)(NMe2)X-2] [X = Cl (4) and Br (5)] by reaction with SiMe3X (X = Cl or Br, respectively). The constrained geometry derivatives [Ti{eta(5)-C5H4SiMe2(eta(1)-NR)}Cl-2] (R = C6H5 6, 2,6-Me2C6H3 7 and 2-Me-6-Pr-i-C6H3 8) 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{eta(5)-C5H4SiMe2[eta(1)-N(C6H3Me2)]}X-2] (X = Me (9), CH2Ph (10), CH2SiMe3 (11) or NMe2 (13)) by metathesis using Grignard or organolithium reagents and into the monoalkyl derivative [Ti{eta(5)-C5H4SiMe2[eta(1)-N(C6H3Me2)]}MeCl] (12) by reaction with AlMe3. The molecular structure of complex 7 [Ti{eta(5)C(5)H(4)SiMe(2)[eta(1)-N(2,6-Me2C6H3)]}Cl-2] was established by X-ray crystallography. (C) 1998 Elsevier Science S.A. All rights reserved.