Metal-ion redox cooperativity is a recurrent theme in small molecule binding to and activation by metal surfaces, cluster cofactors in biology, and various homogeneous synthetic catalysts. Although readily identified when present, the criteria that allow for and control cooperative reactivity are incompletely understood, and partly hindering the design and use of cheaper 3d metals in catalysts for multi-electron redox transformations. Results from our efforts to use ligand design to dictate cooperativity in polynuclear transition metal complexes and the observed resultant small molecule activation will be presented.