Ti IV Complexes with Novel, Chiral, Tridentate Amido‐Amidinate or Monoanionic, Didentate Amidinate Ligands

Reaction of LiL or a new type of dianionic ligand Li 2 L ( 2 ) {H 2 L = (1 R ,2 R )‐(−)‐1‐[N(H)C(Ph)N(SiMe 3 )]‐2‐[N(H)SiMe 3 ]C 6 H 10 } with TiCl 2 (O i Pr) 2 yielded the novel complexes [TiCl(L)(O i Pr) 2 ] ( 1 ) and [Ti(L)(O i Pr) 2 ] ( 3 ), respectively. Treatment of Na 2 L′ {H 2 L′ = (1 R ,2 R )‐(−)‐1,2‐[N(H)C(Ph)N(SiMe 3 )] 2 C 6 H 10 ]} with Ti(O i Pr) 2 Cl 2 unexpectedly gave 3 via a unusual rearrangement/elimination reaction; The structure of complex 3 shows both an η 3 ‐π bond and σ‐bonds to the central metal. This is a new coordination model and is obtained for the first time for this type of amido‐amidinate complex. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)