Isovalent Ag III /Ag III , Ag II /Ag II , Mixed-Valent Ag II /Ag III , and Corrolato-Based Mixed-Valency in β,β'-Linked [Bis{corrolato-silver}] n 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 AgII /AgIII 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 AgII /AgIII and an isovalent AgII /AgII form. Additionally, characterization of the AgIII /AgIII 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.