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

Abstract

Coordination of ar edox-active pyridine aminophenol ligand to Ru II followed by aerobic oxidation generates two diamagnetic Ru III species [1a (cis) and 1b (trans)] with ligand-centered radicals.T he reaction of 1a/1b with excess NaN 3 under inert atmosphere resulted in the formation of arare bis(nitrido)-bridged trinuclear ruthenium complex with two nonlinear asymmetrical Ru-N-Ru fragments.T he spontaneous reduction of the ligand centered radical in the parent 1a/ 1b supports the oxidation of an itride (N 3À )t oh alf an equivalent of N 2 .T he trinuclear omplex is reactive toward TEMPO-H, tin hydrides,t hiols,and dihydrogen.

Localized Mixed‐Valence and Redox Activity within a Triazole‐Bridged Dinucleating Ligand upon Coordination to Palladium

“…Besides the emerging research direction to use redox-active ligand systemsa se lectron reservoirs for bond activation and catalysis, [11,12] these organic fragments are also frequentlye mployed in the synthesis of mixed-valence systems. [13] Twom ain strategies involving the use of redox-activel igands have been pursuedt od ate ( Figure 1): i) mononuclear systems bearing separater edox-active ligandso rt ethered redox-active pockets within the same ligand amenable to controlled and independent redox-switching [14] and ii)dinuclearc omplexes with redox-active metal centers and ar edox-active organic bridging unit.…”