SYNTHESIS, STRUCTURE AND CHARACTERIZATION OF ZINC(II), COPPER(II), ZINC(II) BARIUM(II) AND COPPER(II) BARIUM(II) COMPLEXES OF MACROCYCLIC HETERONUCLEATING LIGANDS BASED ON ISOTHIOSEMICARBAZIDE

The linear polyether dialdehydes 3-yl)-O-(CH2CH2O)(n)-(3-yl-2-hydroxyb enzaldehyde), where n=3 (1), 4 (2), react with S-methylisothiosemicarb azide hydroiodide (or hydrochloride) in the presence of Ba(CF,SO,), an d zinc(II) acetate and/or copper(II) acetate in methanol/THF to give [ (ZnBaLI)-I-1(CF3SO3) (CH3OH)](2). 0.5H(2)O (5), [CuBaL1(CF3SO3)(2)](2) (8) and [CuBaL2(CF3SO3)(2)](2) (10). Treatment of 5 with AgCF3SO3 in methanol and subsequent recrystallization from ethanol results in loss of I- to give [ZnBaL1 (CF3SO3)(2)(H2O)](2) (6). Removal of the Ba2+ f rom 6, 8 and 10 by using an aqueous solution of guanidinium sulfate af fords ZnL1. H2O (7), CuL1. 2H(2)O (9) and CuL2. 2H(2)O (11). The molec ular structure of 5 has been determined by X-ray crystallography. Crys tal data for 5: monoclinic, P2(1)/c,a= 9.331(1), b = 15.293(2), c =25. 940(2) Angstrom, beta = 97.94(1)degrees,Z= 2. Electronic and NMR spect ra, the magnetic behavior, ESR and mass spectra, and the electrochemis try of the new compounds are discussed. (C) 1998 Elsevier Science S.A. All rights reserved.