Abstract: | The (E, E)‐dioxime containing a dithia‐dioxa‐diaza macrocyclic moiety 5,6 : 11,12 : 17,18‐tribenzo‐2,3‐bis(hydroxyimino)‐1,4‐diaza‐7,16‐dithia‐10,12‐dioxacyclooctadecane ( H2L ) has been synthesized in high yield by a 1 + 1 addition of cyanogendi‐N‐oxide with 2,3 : 8,9 : 14,15‐tribenzo‐1,16‐diamino‐4,13‐dithia‐7,10‐dioxahexadecane ( 3 ) which was obtained from condensation reaction with 2‐amino thiophenol and 1,2‐bis(2‐bromoethoxy)benzene, in dichloromethane at –10 °C. Two vic‐Dioxime ligands coordinate with Ni(II), Cu(II) and Co(III) through its hydroxyimino nitrogen donor atoms by the loss of the oxime protons. Homo and heterotrinuclear CuII3 and CoIIIPdII2 complexes of this ligand have been prepared; their two ligand molecules are connected via hydroxyimino or BF2+‐bridging groups and two of the metal ions are coordinated by a diaza‐dithia mixed donor macrocyclic moiety. The macrocyclic ligand and its transition metal complexes have been characterized on the basis of 1H‐, 13C‐NMR, IR and MS spectroscopy and elemental analysis data. |