Molecular examples of mixed-valence copper complexes through chemical oxidation are rare but invoked in the mechanism of substrate activation, especially oxygen, in copper-containing enzymes. To examine the cooperative chemistry between two metals in close proximity to each other we began studying the reactivity of a dinuclear Cu(I) amidinate complex. The reaction of [(2,6-Me2C6H3N)(2)C(H)](2)Cu-2, 1, with I-2 in tetrahydrofuran (THF), CH3CN, and toluene affords three new mixed-valence copper complexes [(2,6-Me2C6H3N) C (H)](2)CU2(mu(2)-I-3) (THF)(2), 2, [(2,6-Me2C6H3N)(2)C (H)(2) Cu-2 (mu(2)-I) (NCMe)(2), 3, and [(2,6-Me2C6H3N)(2)C(H)](3)Cu-3(mu(3)-I)(2), 4, respectively. The first two compounds were characterized by UV-vis and electron paramagnetic resonance spectroscopies, and their molecular structure was determined by X-ray crystallography. Both di- and trinudear mixed-valence intermediates were characterized for the reaction of compound 1 to compound 4, and the molecular structure of 4 was determined by X-ray crystallography. The electronic structure of each of these complexes was also investigated using density functional theory.