Bonding analysis of titanocene borane σ-complexes

Bonding analysis has been performed for complexes Cp2Ti(η2-HBcat)2 and Cp2Ti(PMe3)(η2-HBcat) through the aid of density functional theory calculations at the level of B3PW91. The significantly short B...B contact in the former complex is explained with an unusual three-center-two-electron bond involving the B-Ti-B triangle. In the Cp2Ti(PMe3)(η2-HBcat) complex, a related bonding feature involving a metal d orbital and an sp3-hybridized fragment orbital derived from the HBcat ligand is found to be responsible for the metal-boron interaction.link_to_subscribed_fulltex