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Dancey, Keith Philip (1982) Copper complexes of dinucleating octa-azamacrocyclic ligands. Doctoral thesis, Polytechnic of North London.
The synthesis of mono and dinucleating ligands and their copper complexes are described. Three types of dinacleating tetraimine macrocycles have been prepared from 4,7-diaza-2,3;8,9-dibenzodecane-l,10-dione by condensation with the appropriate polyamine; I, large-ring octa-aza macrocycles e.g. the 28—membered ring compound 5,6,7,8,15,16,23,24,25,26,33,34— dodecahydrotetrabenzo(e,m,s,a’) (1,4,11,15,18,22,25) octaaza- cyclooctacosine and related 30- and 36- membered ring compounds; II, the "fused" bis(tetra-azamacrocycle) 5,6,7,8,22,23,24,25-octahydrotetrabenzo (f,f’1,1’) benzo (1,2-b:4,5-b’)- bis(1,4,8,)tetraazacyclotetradecine; III, the "Linked" bis(tetra-azamacrocycle) 5,6,7,8,24,25,26,27-octahydrotetrabenzo (f,f’,1,1)diphenyl(3,4-b:3’,4’-b’)bis(l,4,8,11)tetraazacyclotetradecine. For the type I and III ligands reduction of the imine linkages yielded the related octa-amines. The preparation of copper complexes is described. For many of the neutral copper complexes (formed by deprotonation of anilino nitrogen atoms) a novel synthetic route had to be used to overcome problems associated with the very low solubility of both ligand and complex.
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