Stabilizing an exotic dianionic tetrazine bridge in a Ln₂ metallocene

The unique electronic nature of the 1,2,4,5-tetrazine or s-tetrazine (tz) ring has sparked tremendous scientific interest over the last few years. Tetrazines have found numerous applications, and their ability to coordinate to metal ions has opened the possibility of exploring their chemistry in both molecular systems and extended networks. The rich redox chemistry of s-tetrazines allows them to exchange electrons and switch between their dihydro (H₂tz), neutral (tz), and radical (tz˙^-) forms. Previous reports in the literature have observed electrochemically that a second electron can potentially be stored in the tetrazinyl ring and form a dianionic species. However, due to its extremely reactive nature, this has not been isolated before. Herein, the combination of strictly anhydrous and inert conditions, strong reducing agents, non-acidic solvents and most importantly blocking the accessibility of the nitrogen atoms by coordinating them to lanthanide ions allowed for the stabilization of a dianionic tetrazine in a lanthanocene complex. Three dinuclear metallocene complexes are reported, [(Cp*₂Ln)₂(tz˙^-)(THF)₂](BPh₄) (Ln = Y (1-Y); Cp* = pentamethylcyclopentadienyl; THF = tetrahydrofuran) and [(Cp*₂Ln)₂(tz^2-)(THF)₂]·2THF (Ln = Gd (2-Gd), or Y (2-Y)), which utilize the unsubstituted tz as the ligand. In 1-Ln, the tz ligand is reduced to the radical anion (tz˙^-), while in 2-Ln, the tz ligand is in the -2 charge state. These complexes are the first structurally and physically characterized complexes bearing the dianion radical of an s-tetrazine. Detailed structural analysis, ab initio calculations, and physical characterization support that the tz^2- ligand is a closed-shell planar dianion with unique structural features vastly different from those of the tz, tz˙^- and H₂tz species.