Synthesis and characterization of novel (<Emphasis Type="Italic">E</Emphasis>,<Emphasis Type="Italic">E</Emphasis>)-dioxime and its mono- and polynuclear metal complexes containing azacrown moieties

The novel (E,E)-dioxime,7,8-bis(hydroxyimino)-1,14-bis(monoaza8]crown-6)-benzof]-4,11-dioxa-1,14-diazadecane7,8-g]quinoxaline (H₂L), has been synthesized by the reaction of 6,7-diamino-1,12-bis(monoaza18]crown-6)benzof]-4,9-dioxa-1,12-diazadecane (4) which has been prepared by the reduction of 6,7-dinitro-1,12-bis(mono-aza18]crown-6)benzof]-4,9-dioxa-1,12-diazdecane (3) and cyanogendi-N-oxide. Mononuclear Ni^II and Cu^II complexes of H₂L have a metal:ligand ratio of 1:2 and the ligand coordinates through two hydroxyimino nitrogen atoms, as do most of the (E,E)-dioximes. The hydrogen-bridged Ni^II complex was converted into its BF ₂ ⁺ capped anologue by the reaction with BF₃ · Et₂O. The reaction of the Cu^II complex with 2,2′-dipyridyl as an end-cap ligand gave the homotrinuclear complex. Structures for the ligand and its complexes are proposed in accordance with elemental analysis, magnetic susceptibility measurements, ¹H, ¹³C-n.m.r, IR and MS spectral data.