Bulky-hindrance-controlled ligand transformation from linked bis(amidinate) to linked imido-amidinate promoted by a mono(cyclopentadienyl)titanium group

Article abstract of DOI:10.1002/ejic.200600658

A novel class of silyl-linked bis(amidinate) ligands [SiMe ₂-{NC(Ph)N(2,6-R₂Ph)Li)₂] [L¹ (R = H), L² (R = Me), and L³ (R = iPr)] reacted with TiCl ₃(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 L¹ and L². It was found that the rearrangement process was related to the steric hindrance of the terminal substituents. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.