Electrochemistry of nickel(II) complexes with N,N′-bis(3,5-di-tert-butylsalicylidene)polymethylenediamines

Abstract

The electrochemical oxidation of several N,N′-polymethylenebis(3,5-di-tert- butylsalicylaldiminato)nickel(II) complexes, Ni(Lx), has been studied by cyclic voltammetry and in situ UV–Vis spectroscopy in DMF. Cyclic voltammograms of Ni(Lx) (x = 1–4) complexes displayed two-step oxidation processes under nitrogen gas atmosphere. The first oxidation peak potentials of all the Ni(II) complexes corresponds to the reversible one-electron oxidation process of the metal center, yielding Ni(III) species. EPR spectrum of the electrolysis solution was recorded after one electron transfer at liquid nitrogen temperature also confirms the formation of [NiIII(L3)]+ species (gx > gy > gz) with a 2A1(dz2)1 ground state. Upon addition of pyridine to one electron oxidised solutions a new penta coordinated species, [NiIII(L3)Py]+ (g⊥ > g∥, a∥(14N) = 8 G), was produced. The second oxidation peak of the complexes was assigned as the ligand based oxidation, generating a coordinated phenoxy radical species.