On the border between localization and delocalization: tris(iminoxolene)titanium( iv )

This is the authors' abstract. We don't add key points for this paper.

The tris(aminophenol) ligand tris(4-methyl-2-(3',5'-di-tert-butyl-2'-hydroxyphenylamino)phenyl)amine, MeClampH6, reacts with Ti(OiPr)4 to give, after exposure to air, the dark purple, neutral, diamagnetic complex (MeClamp)Ti. The compound is six-coordinate, with an uncoordinated central nitrogen (Ti-N = 2.8274(12) Å), and contains titanium(iv) and a doubly oxidized ligand, formally a bis(iminosemiquinone)-mono(amidophenoxide). The compound is unsymmetrical in the solid state, though the three ligands are equivalent on the NMR timescale in solution. Ab initio calculations indicate that the ground state is a multiconfigurational singlet, with a low-lying multiconfigurational triplet state. Variable-temperature NMR measurements are consistent with a singlet-triplet gap of 1200 ± 70 cm-1, in good agreement with calculations. The distortion from threefold symmetry allows a low-lying, partially populated ligand-centered π nonbonding orbital to mix with largely occupied metal-ligand π bonding orbitals. The energetic accessibility of this distortion is inversely related to the strength of the metal-ligand π bonding interaction.