Reaction of [Ru-VI(N)(L-1)(MeOH)](+) (L-1 = N,N'-bis(salicylidene)-o-cyclohexylenediamine dianion) with excess pyridine in CH3CN produces [Ru-III(L-1)(py)(2)](+) and N-2. The proposed mechanism involves initial equilibrium formation of [Ru-VI(N)(L-1)(py)](+), which undergoes rapid N center dot center dot center dot N coupling to produce [(py)(L-1) (RuN)-N-III N-Ru-III(L-1) (py)](2+); this is followed by pyridine substituion to give the final product. This ligand-induced N center dot center dot center dot N coupling of Ru-VI N is utilized in the preparation of a series of new ruthenium(III) salen complexes, [Ru-III(L)(X)(2)] +/- (L = salen ligand; X = H2O, 1-Melm, py, Me2SO, PhNH2, (BuNH2)-Bu-t, Cl- or CN-) The structures of [Ru-III(L-1)(NH2Ph)(2)](PF6) (6), K[Ru-III(L-1)(CN)(2)] (9), [Ru-III(L-2)(NCCH3)(2)][Au-1(CN)(2)] (11) (L-2 = N,N'-(-bis(salicylidene)-o-phenylenediamine dianion) and [(NBu4)-Bu-n][Ru-III(L-3)Cl-2) (12) (L-3 = N,N-bis(salicylidene)ethylenediamine dianion) have been determined by X-ray crystallography.