A theoretical analysis of [M(tmtaa)] and [M(acacen)] fragments employed in the organometallic chemistry of early transition metals

The [M(tmtaa)] and [M(acacen)] fragments employed in the organometallic chemistry of titanium and vanadium have been investigated by a density functional approach. The frontier orbitals and the geometrical structure of the two macrocyclic ligands have been compared and the effect of the nature of the metal on the ligand environments has been studied. Some interesting complexes in which the metal contains a reactive organometallic functionality, such as metal–halogen (F and Cl) or metal–alkyl (CH3) units, have been investigated. Moreover, the [Mo(acacen)]2 dimer has been considered because of its interest as a metalmetal bonded complex with non-bridging ligands restraining the metalmetal distance.