Group 3 metal complexes of radical-anionic 2,2'-bipyridyl ligands

A new method for generating group 3 metal complexes containing radical-anionic 2,2'-bipyridyl (bipy) ligands is described that relies on hydrogen-atom abstraction from dearomatized biheterocyclic complexes. This method does not involve electron transfer to neutral 2,2'-bipyridyl or salt metathesis between the lithium salt of the 2,2'-bipyridyl radical anion and group 3 metal halides. The new metal complexes were characterized by single-crystal X-ray diffraction, electron paramagnetic resonance, and absorption spectroscopy. Density functional theory (DFT) calculations were used to probe the electronic structure of these compounds. All these methods support the radical-anionic character of bipy in all bipy compounds presented.