Structural and redox properties in thioether-based (N/S) copper(II/I) complexes: Experimental and theoretical investigations

The complexes [CuIN2(SMe)2](ClO4) (1) and [CuIIN2(SMe)2(CF3SO3)2] (2) in both CuI and CuII redox states from N2(SMe)2 ligand (N,N-(2-pyridylmethyl)bis(2-methyl-thiobenzyl)amine) have been synthesized and structurally characterized by X-ray crystallography. Electrochemical studies show that the two complexes interconvert during the one electron transfer. Comparison with another complex with tBu instead Me groups on the thioether ligand shows detectable changes in X-ray structures and in redox properties. Theoretical calculations on the different steps of the redox process have been performed. Values underline steric constraints induced by the substitutions on thioether alkyl groups.