SYNTHESIS AND COMPLEX FORMATION OF NOVEL 12-MEMBERED MACROCYCLIC (E,E)-DIOXIMES

Abstract
Dibenzo[e,k]-2,3-bis(hydroxyimino) 1.4.7.10-tetrathia-2,3,8,9-tetrahydrocyclododecine (S4H2) and dibenzo-[e,k]-2,3-bis(hydroxyimino)-1,4-dithia-7,10-dioxa-2,3,8,9- tetrahydrocyclododecine (O2S2H2) have been prepared from (E,E)-dichloroglyoxime, 2,3,8,9-dibenzo-1,4,7,10-tetrathiadecane (DTT) and 2,3,8,9-Dibenzo-4,7-dioxa-1,10-dithiadecane (DDD) which was synthesized by treating 1,2-bis(o-aminophenoxy)ethane with HNO2 and potassium ethylxsanthate. The structures of these vic-dioximes have been determined as the (E,E)-forms according to 1H-NMR and IR data. Only mononuclear complexes with a metal-ligand ratio of 1:2 have been isolated with Co(II), such as [(S4H)2Co(III)L′Cl] and [(O2S2H)2Co(III)L′Cl]; Cu(II) forms only trinuclear complexes. Reaction of the mononuclear complexes with Pd(II) gives heterotrinuclear complexes.

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