Mono- and polynuclear neutral complexes have been obtained by direct electrochemical reaction of metal anodes with the potentially heptadentate and tetracompartmental ligand N,N′-bis(3-hydroxysalicylidene)-1,3-diamino-2-propanol (H 5 L). Physicochemical data suggest that the ligand behaves as a di- or tetra-anion in mono- and polynuclear complexes, respectively. Metal ions are held together by μ-phenoxo oxygen bridges in polynuclear complexes. Nickel and copper environments are distorted to tetrahedral and square-planar, respectively. Zinc and cadmium could be hexa-coordinated in the mononuclear complexes. Finally, iron and cobalt ions seem to be in pseudo-octahedral fields.