Structure, Spectroscopy, and Reactivity of a Mononuclear Copper Hydroxide Complex in Three Molecular Oxidation States.

Structural, spectroscopic, and reactivity studies are presented for an electron transfer series of copper hydroxide complexes supported by a tridentate redox-active ligand. Single crystal X-ray crystallography shows that the mononuclear [CuOH]1+ core is stabilized via intramolecular H-bonds between the H-donors of the ligand and the hydroxide anion when the ligand is in its trianionic form. This complex undergoes two reversible oxidation processes that produce two metastable "high-valent" CuOH species, which can be generated by addition of stoichiometric amounts of 1e- oxidants. These CuOH species are characterized by an array of spectroscopic techniques including UV-vis absorption, electron paramagnetic resonance (EPR), and X-ray absorption spectroscopies (XAS), which together indicate that all redox couples are ligand-localized. The reactivity of the complexes in their higher oxidation states toward substrates with modest O-H bond dissociation energies (e.g., 4-substitued-2,6-di-tert-butylphenols) indicates that these complexes act as 2H+/2e- oxidants, differing from the 1H+/1e- reactivity of well-studied [CuOH]2+ systems.