Copper versus thioether-centered oxidation: mechanistic insights into the non-innocent redox behavior of tripodal benzimidazolylaminothioether ligands.

A series of Cu(+) complexes with ligands that feature varying numbers of benzimidazole/thioether donors and methylene or ethylene linkers between the central nitrogen atom and the thioether sulfur atoms have been spectroscopically and electrochemically characterized. Cyclic voltammetry measurements indicated that the highest Cu(2+)/Cu(+) redox potentials correspond to sulfur-rich coordination environments, with values decreasing as the thioether donors are replaced by nitrogen-donating benzimidazoles. Both Cu(2+) and Cu(+) complexes were studied by DFT. Their electronic properties were determined by analyzing their frontier orbitals, relative energies, and the contributions to the orbitals involved in redox processes, which revealed that the HOMOs of the more sulfur-rich copper complexes, particularly those with methylene linkers (-N-CH2-S-), show significant aromatic thioether character. Thus, the theoretically predicted initial oxidation at the sulfur atom of the methylene-bridged ligands agrees with the experimentally determined oxidation waves in the voltammograms of the NS3- and N2S2-type ligands as being ligand-based, as opposed to the copper-based processes of the ethylene-bridged Cu(+) complexes. The electrochemical and theoretical results are consistent with our previously reported mechanistic proposal for Cu(2+)-promoted oxidative C-S bond cleavage, which in this work resulted in the isolation and complete characterization (including by X-ray crystallography) of the decomposition products of two ligands employed, further supporting the novel reactivity pathway invoked. The combined results raise the possibility that the reactions of copper-thioether complexes in chemical and biochemical systems occur with redox participation of the sulfur atom.