Bulky‐Hindrance‐Controlled Ligand Transformation from Linked Bis(amidinate) to Linked Imido‐Amidinate Promoted by a Mono(cyclopentadienyl)titanium Group

A novel class of silyl‐linked bis(amidinate) ligands [SiMe 2 {NC(Ph)N(2,6‐R 2 Ph)Li} 2 ] [ L 1 (R = H), L 2 (R = Me), and L 3 (R = i Pr)] reacted with TiCl 3 (C 5 H 5 ) to produce the half‐sandwich titanium complexes 1 , 2 , and 3 . The molecular structures of 1 – 3 were confirmed successfully by X‐ray crystallography. An unprecedented intramolecular ligand transformation from the linked bis(amidinate) configuration to the linked imido‐amidinate configuration took place in the cases of L 1 and L 2 . It was found that the rearrangement process was related to the steric hindrance of the terminal substituents. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)