Metal Complexes of 22-Niembered Mononuclear Tetraimine-Tetraamide Macrocycles: Synthesis and Characterization

Abstract

Template condensation reaction of succinic acid or phthalic acid with hydrazine hydrate and 2,4-pentanedione resulted in the formuation of a new series of 22-membered tetraiminetetraamide macrocyclic complexes: dichloro/dinitrato (8, 11, 19, 22-tetraone-3, 5, 14, 16-tetramethyl-1, 2, 6, 7, 12, 13, 17, 18-octaazacyclodocosane-2, 5, 13, 16-tetraene)metal(II), [ML1X2] [M = Mn(II), Co(II), Ni(II) and Zn(II); X = CI or NO3]; (8, 11, 19, 22-tetraone-3, 5, 14, 16-tetramethyl-1, 2, 6, 7, 12, 13, 17, 18-octaazacyclodocosane-2, 5, 13, 16-tetraene)copper(II) dichloride/dinitrate [CuL1]X2; dichloro/dinitrato(9, 10, 20, 21-d ibenzo-8, 11, 19, 22-tetraone-3, 5, 14, 16-tetramethyl-1, 2, 6, 7, 12, 13, 17, 18-octaazacyclodocosane-2, 5, 13, 16-tetraene)metal(II), [ML2X2] [M = Mn(II), Co(II), Ni(II) and Zn(II); X = CI or NO3) and (9, 10, 20, 21-dibenzo-8, 11, 19, 22-tetraone-3, 5, 14, 16-tetramethyl, 2, 6, 7, 12, 13, 17, 18-octaazacyclodocosane-2, 5, 13, 16-tetraene)copper(II) dichloride/dinitrate, [CuL2]X2. These complexes have been characterized by IR, 1H NMR, EPR and electronic spectral studies, conductivity and magnetic susceptibility measurements. An octahedral geometry has been suggested for the manganese, cobalt, nickel and zinc complexes, while a square-planar geometry is proposed for the copper complexes. All complexes are stable to air.