Rapid Access to Dimethylcyclopentadienyltitanium(IV) Amidinate, (C5R5)TiMe2[NR1C(R2)NR3] (R = H and Me; R2 = Me), Libraries

Facile insertion of carbodiimides, R 1 N C NR 3, into a Ti−C Me bond of (C 5 R 5 )TiMe 3 (R = H and Me) ( 2a and 2b, respectively) in pentane solutions at 25 °C provides a wide range of derivatives of (C 5 R 5 )TiMe 2 [NR 1 C(Me)NR 3 ] ( 1 ) in high yield. Low barriers to racemization (≤15 kcal mol -1 ) have been determined for derivatives of 1 where R 1 ≠ R 3, and further, a preliminary screen has found some of these to be Ziegler−Natta catalyst precursors for the polymerization of ethylene upon activation with methylaluminoxane.