"Double redox-activity" in azobenzene-quinonoid palladium(II) complexes:: a combined structural, electrochemical and spectroscopic study

Abstract

Reactions of [(az-H)Pd(μ-Cl)2Pd(az-H)] (az = azobenzene) with the zwitterionic, p-benzoquinonemonoimine-type ligands 4-(n-butylamino)-6(n-butylimino)-3-oxocyclohexa-1,4-dien-1-olate (Q1) or 4-(isopropylamino)-6(isopropylimino)-3-oxocyclohexa-1,4-dien-1-olate) (Q2) in the presence of a base leads to the formation of the mononuclear complexes [(az-H)Pd(Q1-H)] (1) and [(az-H)Pd(Q2-H)] (2) respectively. Structural characterization of 2 shows an almost square planar coordination geometry around the Pd(II) centre, a short Pd–C bond, a slight elongation of the N[double bond, length as m-dash]N double bond of the az-H ligand and localization of the double bonds within the Q2-H ligand. Additionally, intermolecular N–H–O interactions exist between the uncoordinated N–H and O groups of two different molecules. Cyclic voltammetry of the complexes reveals an irreversible oxidation and two reversible reduction processes. A combination of electrochemical and UV-vis-NIR and EPR spectroelectrochemical studies are used to show that both coordinated ligands participate successively in the redox processes, thus revealing their non-innocent character.