Redox‐Active‐Ligand‐Mediated Formation of an Acyclic Trinuclear Ruthenium Complex with Bridging Nitrido Ligands

Coordination of a redox‐active pyridine aminophenol ligand to Ru II followed by aerobic oxidation generates two diamagnetic Ru III species [ 1 a (cis) and 1 b (trans)] with ligand‐centered radicals. The reaction of 1 a / 1 b with excess NaN 3 under inert atmosphere resulted in the formation of a rare bis(nitrido)‐bridged trinuclear ruthenium complex with two nonlinear asymmetrical Ru‐N‐Ru fragments. The spontaneous reduction of the ligand centered radical in the parent 1 a / 1 b supports the oxidation of a nitride (N 3− ) to half an equivalent of N 2 . The trinuclear omplex is reactive toward TEMPO‐H, tin hydrides, thiols, and dihydrogen.