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)RuII–CN–RuII/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 RuII–CN–RuIII is the one-electron oxidized product of 1+ with RuII–CN–RuII. 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.