The synthesis and characterization of novel (E,E)-dioximes and their mono- and heteronuclear complexes

Two new macrocyclic vic-dioximes, 5,6:9,10:13,14-tribenzo-2,3-bis(hydroxyimino)-1,4-dithia-7,12-diazacyclotetradecane (H(2)L(1)) and 5,6:9,10:13,14-tribenzo-2,3-bis(hydroxyimino)1,4-diaza-7,12-dithiacyclotetradecane (H(2)L(2)) have been synthesized by the reaction of (E E)-dichloroglyoxime with alpha,alpha'-bis(o-mercaptophenylamino)-1,2-xylene or alpha,alpha'-bis(o-aminophenylthio)-1,2-xylene, respectively, The mononuclear Co(III) complexes of these dioximes have been isolated with L'=pyrimidine, together with chlorine as an axial ligand. In addition, new Co(III) complexes which contain the bridging BF2+ were synthesized with these ligands. Heterotrinuclear complexes of these Br2+-capped cobalt(III) complexes have also been obtained by the reaction of BF2(+)-bridged combalt(III) complexes with Po[bis(benzonitrile)]Cl-2. The structure of dioximes and complexes and electrochemical properties were identified by using elemental analysis, C-13, H-1 NMR, IR and MS spectral data and cyclic voltammetry.