Synthesis and characterization of a novel (E,E)-Dioxime and its mono and Heterotrinuclear complexes containing a 15-membered Dioxatrithiamacrocycle ligand with transition metals

Abstract

A new macrocyclic vic-dioxime, 1,3-bis(benzo-7,9,13-trithia-1,4-dioxacyclopentadecane)-2-thioxo-4,5-bis- (hydroxyimino)imidazoline (H₂L) has been synthesized by reaction of (E,E)-dichloroglyoxime (3) with N,N′-bis(benzo-7,10,13-trithia-1,4-dioxa-cyclopentadecane)thiourea (2), which was prepared from 2,3-(4′-aminobenzo)-7,10,13-trithia-1,4-dioxacyclopentadecane and thiocarbonyldichloride. The mononuclear Ni(II) complex of H₂L, [Ni(HL)₂], (4) has been prepared by reaction of H₂L with nickel(II) chloride hexahydrate. The mononuclear Co(III) complex of the dioxime [Co(HL)₂P(Ph)₃Cl] (5) has been isolated with triphenylphospine and chloride as axial ligands. In addition, a Co(III) complex containing the bridged macrocycle [Co(LBF₂)₂P(Ph)₃Cl] (6) was synthesized using a precursor hydrogen-bridged Co(III) complex via the template effect. The heterotrinuclear complex of the -capped Co(III) complex [Ag₂Co(LBF₂)₂ P(Ph)₃Cl](CH₃COO)₂ (7) has also been prepared by reaction of this complex with Ag(CH₃COO). The structures of the dioxime and its complexes were identified by elemental analysis together with ¹H and ¹³C NMR, IR and mass spectral data.