Tuning Inner-Sphere Electron Transfer in a Series of Copper/Nitrosoarene Adducts

A series of copper/nitrosoarene complexes was created that mimics several steps in biomimetic O₂ activation by copper(I). The reaction of the copper(I) complex of N,N,N',N'-tetramethypropylenediamine with a series of para-substituted nitrosobenzene derivatives leads to adducts in which the nitrosoarene (ArNO) is reduced by zero, one, or two electrons, akin to the isovalent species dioxygen, superoxide, and peroxide, respectively. The geometric and electronic structures of these adducts were characterized by means of X-ray diffraction, vibrational analysis, ultraviolet-visible spectroscopy, NMR, electrochemistry, and density functional theory (DFT) calculations. The bonding mode of the NO moiety depends on the oxidation state of the ArNO moiety: κN for ArNO, mononuclear η²-NO and dinuclear μ-η²:η¹ for ArNO^•-, and dinuclear μ-η²:η² for ArNO^2-. ¹⁵N isotopic labeling confirms the reduction state by measuring the NO stretching frequency (1392 cm^-1 for κN-ArNO, 1226 cm^-1 for η²-ArNO^•-, 1133 cm^-1 for dinuclear μ-η²:η¹-ArNO^•-, and 875 cm^-1 for dinuclear μ-η²:η² for ArNO^2-). The ¹⁵N NMR signal disappears for the ArNO^•- species, establishing a unique diagnostic for the radical state. Electrochemical studies indicate reduction waves that are consistent with one-electron reduction of the adducts and are compared with studies performed on Cu-O₂ analogues. DFT calculations were undertaken to confirm our experimental findings, notably to establish the nature of the charge-transfer transitions responsible for the intense green color of the complexes. In fine, this family of complexes is unique in that it walks through three redox states of the ArNO moiety while keeping the metal and its supporting ligand the same. This work provides snapshots of the reactivity of the toxic nitrosoarene molecules with the biologically relevant Cu(I) ion.