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 [SiMe2{NC (Ph)N(2,6-R2Ph)Li)(2)] [L-1 (R = H), L-2 (R = Me), and L-3 (R = iPr)] reacted with TiCl3(C5H5) 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. (c) Wiley-VCH Verlag GmbH & Co.