DICOPPER(II) COMPLEXES OF SPIRO MACROBICYCLES WITH AZA AND THIA AZA DONOR SETS

Reaction of the dicopper(II) complex of the binucleating ligand 5, 5-bis(4-amino-2-azabutyl)-3, 7-diazanonane-1, 9-diamine with nitroethane and formaldehyde in water gives the respective macrobicyclic and macromonocyclic binucleating ligands 7, 21-dimethyl-7, 21-dinitro-2, 5, 9, 12, 16, 19, 23, 26-octaazaspiro[13.13]heptacosane and 6, 6-bis(4-amino-2-azabutyl)-13-methyl-13-nitro-l, 4, 8, 11-tetraazacyclotetradecane, both as their dicopper(II) complexes. Similarly, condensation of the dicopper(II) complex of 5, 5-bis(4-amino-2-thiabutyl)-3, 7-dithianonane-1, 9-diamine with nitroethane and formaldehyde results in the binucleating macrobicycle 7, 21-dimethyl-7, 21-dinitro-2, 12, 16, 26-tetrathia-5, 9, 19, 23-tetraazaspiro[13.13]-heptacosane. Physical properties of all complexes are reported and comparisons with mononuclear relatives are made. Structural parameters derived from electron paramagnetic resonance spectra are discussed. © 1990 ASEG.