A Combined Spectroelectrochemical and Computational Study of the Chemically Reversible 2-Electron Reduction of [Ru-4(Mu-rc2r)(2)(co)(11)] Clusters

The 62-CVE clusters Ru-4(mu-RC2R)(2)(CO)(11), which feature a dodecahedral cluster core, are readily reduced to a 64-CVE dianion in a process that is essentially chemically reversible. A combination of electrochemical, spectroelectrochemical, and computational analyses of the system indicates that the first formed dianion, which features a square planar arrangement of the metal centers with the alkyne ligands located on opposite faces of the M-4 square and oriented in a manner such that the C-C bonds are perpendicular to each other, undergoes a thermal rearrangement giving a product in which the alkyne vectors lie parallel to each other across the metal framework.