Dicopper(II) Complexes of Spiro Macrobicycles With Aza and Thia Aza Donor Sets

Abstract

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-1,4,8,11-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.