Synthesis and characterization of (3,1) Ru2(F3aP)4(NCS) and (3,1) Ru2(F3ap)3(F2Oap)(NCS) where F3ap is the 2-(2,4,6-trifluoroanilino)pyridinate anion

Two isothiocyanate diruthenium complexes, (3,1) Ru-2(F(3)ap)(4)(NCS) 1 and (3,1) Ru-2(F(3)ap)(3)(F(2)Oap)(NCS) 2 (where F(3)ap = 2,4,6-trifluoroanilinopyridinate anion), were synthesized from (3,1) Ru-2(F(3)ap)(4)Cl and SCN- under different experimental conditions. Each compound was examined as to its structural, electrochemical, spectroscopic, and magnetic properties. Compound 1 contains three unpaired electrons as its parent compound but 2 is diamagnetic. The X-ray molecular structures of 1 and 2 reveal that the NCS group is coordinated to the dimetal unit via nitrogen in both compounds with the Ru-N-C bond angle being 176.5 degrees for 1 and 166.0 degrees for 2. An elongation of the Ru-Ru bond distance and a shortening of both the Ru-N-p (p = pyridyl) and the Ru-N-a (a = anilino) bond lengths is seen upon going from (3,1) Ru-2(F(3)ap)(4)Cl to 2, but the conversion of (3,1) Ru-2(F(3)aP)(4)Cl to 1 does not affect significantly structural features of the Ru-2(L)(4) framework. Compound 1 undergoes one reduction and two oxidations, all three of which involve the dimetal core, whereas 2 undergoes two metal-centered reductions, one-metal-centered oxidation, and one ligand-based oxidation due to the presence of the F(2)Oap ligand on the Ru-2 complex. The reactivity of 1 with SCN- was also investigated.