Isovalent Ag /Ag , Ag /Ag , Mixed-Valent Ag /Ag , and Corrolato-Based Mixed-Valency in β,β'-Linked [Bis{corrolato-silver}] Complexes.

Mixed-valent compounds are fascinating entities that are useful as models for investigating electron-transfer reactions, and find use in a host of biologically relevant redox processes. Though the bio-relevant metal copper is well established in mixed-valent chemistry, the Ag /Ag mixed-valent combination of its higher congener in a molecular complex has rarely been reported before. This work reports the synthesis of a new β,β'-linked bis{corrolato-silver(III)} complex and its characterization in five different redox states. A combination of electrochemistry, spectroelectrochemistry, and DFT calculations point to the existence of a mixed-valent Ag /Ag and an isovalent Ag /Ag form. Additionally, characterization of the Ag /Ag form and ligand-based corrolato-centered mixed-valency is presented as well. These results thus open new avenues for bis-corrolato ligands and for mixed-valency in disilver compounds.