Class III Delocalization in a Cyanide-Bridged Trimetallic Mixed-Valence Complex

The NIR and IR spectroscopic properties of the cyanide-bridged complex, trans-[Ru(dmap)(4){(mu-CN)Ru(py)(4)Cl}(2)](3+) (py=pyridine, dmap=4-dimethylaminopyridine) provide strong evidence that this trimetallic ion behaves as a Class III mixed-valence species, the first example reported of a cyanide-bridged system. This has been accomplished by tuning the energy of the fragments in the trimetallic complex to compensate for the intrinsic asymmetry of the cyanide bridge. Moreover, (TD)DFT calculations accurately predict the spectra of the trans-[Ru(dmap)(4){(mu-CN)Ru(py)(4)Cl}(2)](3+) ion and confirms its delocalized nature.