Synthetic, structural, electrochemical and electronic characterisation of heterobimetallic bis(acetylide) ferrocene complexes

A series of novel heterobimetallic bis(acetylide) ferrocene complexes featuring a bis[1,2-bis(diphenylphosphino)methane]ruthenium centre and seven variously substituted aromatic acetylene ligands have been synthesised and characterised. The crystal structure of trans-[Ru(dppm) 2 {CC(C 5 H 4 )Fe(C 5 H 5 )} 2 ] shows the ruthenium centre in a distorted-octahedral environment bound to two ferrocene units in a linear fashion by ‘rigid-rod’-like acetylene linkages. The conformation is stabilised by strong intramolecular CH· · ·π(CC) interactions. Electrochemical studies showed that incorporation of donor-substituted aromatic acetylide ligands causes a cathodic shift in the Ru II/III redox potential. Conversely, an anodic shift is observed when electron-withdrawing substituents are present in the acetylide systems. Electronic spectral measurements indicated that the systems belong to the Robin and Day ‘Class II’ mixed-valence species and suggest that greater electronic interaction occurs in the bis(acetylide) complexes than in the corresponding monoacetylide chloro-complex.