Characterization of the one-electron oxidized Cu(II)-salen complexes with a side chain aromatic ring: the effect of the indole ring on the Cu(II)-phenoxyl radical species

To gain insights into the role of the proximal indole ring in the redox-active metal center as seen in galactose oxidase, we prepared the Cu(II)-salen-type complexes having a pendent indol-3-ylmethyl (1), methyl (2) or benzyl (3) group substituted on the ethylenediamine moiety and investigated the structures and redox properties by various physicochemical methods and theoretical calculations. Neutral complexes 1, 2, and 3 showed no significant difference in the UV–Vis–NIR and EPR spectra. One-electron oxidation of 1, 2, and 3 by addition of 1 equiv. of thianthrenyl radical gave [1]SbCl ₆ , [2]SbCl ₆ , and [3]SbCl ₆ , respectively, which could be assigned to relatively localized phenoxyl radical species. The cyclic and differential pulse voltammograms of [1]SbCl ₆ showed two redox waves with a large separation between the first and second redox potentials compared with the separations observed for [2]SbCl ₆ and [3]SbCl ₆ . This suggests that [1]SbCl ₆ is more stabilized than [2]SbCl ₆ and [3]SbCl ₆ . The NIR band of [1]SbCl ₆ showed a larger blue shift than that of [2]SbCl ₆ and [3]SbCl ₆ . The EPR spectrum of [2]SbCl ₆ exhibited an intense signal at the g value of 2 due to partial disproportionation to form the EPR active two-electron oxidized complex [2] ²⁺ , while the EPR intensity of [1]SbCl ₆ was much weaker than that of [2]SbCl ₆ . These results indicate that the pendent indole moiety stabilizes the Cu(II)-phenoxyl radical in [1]SbCl ₆ most probably by stacking with the phenoxyl moiety, which is further supported by DFT calculations.