Reaction of a (Salen)ruthenium(VI) Nitrido Complex with Isocyanide

The treatment of [RuVI(N)(L)(MeOH)]PF6 (1) (L = N,N′-bis(salicylidene)-o-cyclohexyldiamine dianion) with 2 equiv of RNC (R = (a) tBu, (b) Cy) in CH2Cl2 affords a mixture of blue cis-β-[RuIII(NCNR)(L)(CNR)] (2) and green trans-[RuIII(L)(CNR)2]PF6 (3) products. The reduction of 3 with a stoichiometric amount of Cp2Co in CH3CN gives red trans-[RuII(L)(CNR)2] (4). Refluxing 4 with 3 equiv of RNC in methanol in the presence of 5 equiv of NH4PF6 affords a yellow complex, mer-[RuII(η3-HL)(CNR)3](PF6) (5), in which the ligand is in an η3-coordination mode. These complexes are characterized by IR, UV−vis, ESI-MS, CV, magnetic measurements, and CHN elemental analysis. The structures of 2a, 3a, 4a, 4b, and 5a have been determined by X-ray crystallography.