SYNTHESIS, SPECTROSCOPIC, MAGNETIC AND ELECTROCHEMICAL PROPERTIES OF CU(II) AND FE(III) COMPLEXES WITH THE NEW LIGAND '-DITHIOBIS(PHENYL)]BIS(5'-METHOXYSALICYLALDIMINE)

The synthesis of '-dithiobis(phenyl)]bis(5'-methoxysalicylaldimine) (5 MeOSalps) is reported, as well as its reactions with Cu(CH3COO)(2) . H 2O and anhydrous FeCl3 to give [Cu(SMeOSalps)], [Cu(SMeOSalps)], or [F eCl(SMeOSalps)], respectively, whose spectroscopic, magnetic, thermogr avimetric, calorimetric and electrochemical properties have been studi ed and discussed in terms of N2O2S- or N2O(3)-type coordination for th e monomeric and the dimeric complexes, respectively, the latter presen ting two bridging phenoxide groups between the two Cu(II) ions. The de pendence of the magnetic susceptibility on the temperature follows the Curie-Weiss law and no interaction between the copper ions is detecte d in the dimeric complex, As indicated by cyclic voltammetry and contr olled potential electrolysis, in aprotic medium, the complexes undergo redox processes involving not only the metal redox pairs Cu(II)/Cu(II I), Cu(II)/Cu(I) or Fe(III)/Fe(II), but also SMeOSalps for which anodi c processes centred at the phenolic or at the disulfide bridge, and ca thodic processes localized at the latter group or at the imine moiety have been observed. The monomeric copper complex undergoes a chemicall y reversible two-electron reduction (with a quasi-reversible electroch emical character) which has been investigated by digital simulation an d rationalized by considering a reversible molecular rearrangement whi ch could involve the cleavage of a metal-sulfur bond.