Syntheses, Characterizations, and Crystal Structures of Dinitrogen‐Divanadium Complexes Bearing Triamidoamine Ligands

We recently reported the syntheses, crystal structures, and protonation reactions of dinitrogen divanadium complexes bearing triamidoamine ligands, ([{V(LR)}2(µ‐N2)] (R = iBu (1), EtBu (2), and iPr2Bn (3)). In this study, we have additionally synthesized two novel dinitrogen‐divanadium complexes with similar derivatives (R = Bn (4) and MeBn (5)), which are characterized spectroscopically and structurally. The X‐ray structures have both revealed a divanadium complex with a bridging N2 ligand. The protonation reactions of the µ‐N2 ligands for 4 and 5 in the presence of M+[C10H8]– (M+ = Na+, K+) and proton source (HOTf or [LutH](OTf)) have given ammonia. Particularly, the NH3 yield from the reaction of 5 with K+[C10H8]– and [LutH](OTf) has been 341 %. Furthermore, mixed valence Na+ adduct of 1, [Na{V(LiBu)}2(µ‐N2)] (6), which is prepared by the reaction of 1 with sodium metal, has been prepared and its crystal structure has also been determined. Compound 6 is electrochemically and spectroscopically characterized, which is also evaluated by DFT calculation method. Two novel µ‐dinitrogen‐divanadium complexes with triamidoamine derivatives have been characterized spectroscopically and structurally. The protonation reactions of the µ‐N2 ligands for them have given ammonia. Furthermore, the mixed valence Na+ adduct of the dinitrogen complex has been prepared and characterized. It is also evaluated by DFT calculations.