A Class III asymmetric binuclear cyanido-bridged mixed-valence complex

Abstract

In this work, we report a pair of asymmetric cyanido-bridged binuclear Ru–CN–Ru–Cl complexes, [Cp*(dppe)Ru^II–CN–Ru^II/III(bpy)₂Cl]ⁿ⁺[BF₄]_n (1ⁿ⁺[BF₄]_n, n = 1, 2; Cp* = 1,2,3,4,5-pentamethylcyclopentadiene, dppe = 1,2-bis(diphenylphosphino)ethane, bpy = 2,2′-bipyridine), and 1²⁺ with Ru^II–CN–Ru^III is the one-electron oxidized product of 1⁺ with Ru^II–CN–Ru^II. Both the complexes are well characterized. The investigations indicate that 1²⁺ is a completely delocalized (Class III) mixed-valence complex, confirmed by theoretical calculations. To the best our knowledge, 1²⁺ is the first example of the structurally characterized asymmetric cyanido-bridged Class III mixed-valence complex.