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Judd, P. M. (1982) Tetraazamacrocyclic ligands and their copper complexes. Doctoral thesis, Polytechnic of North London.
The preparation and characterisation of several new types of tetraazamacrocycles and their copper(ll) complexes are described. Condensations of 4,8-diaza-2,3:9,10-dibenzoundecane-1,11-dione with a range of aliphatic and aromatic diamines has allowed the isolation of metal-free diimine macrocycles without recourse to metal template' or 'high dilution' techniques. In several cases these diimines were successfully reduced to yield the related tetraamine macrocycles.
For the 15-membered macrocycle, 18,19,20,21-tetrahydro-17-H-tribenzo(f,j,n)(1,5,9,12)tetraazacyclopentadecine, derivatives bearing different substituents in one of the benzene rings were prepared. For the diimine ligands of this type both cationic and neutral copper(II) complexes were isolated and characterised; (the latter type result from loss of anilino protons on complex formation.)
Compounds which are structurally related to the above tetraazamacrocycles are described. C-alkylation of the diimines using organolithium reagents appears to proceed regioselectively. An X-ray structure determination of the copper complex of 5,12-dimethyl-5,6,11,12, 18,19,20,21-octahydro-17-H-tribenzo (f,j,n)(1,5,9,12) tetraazacyclopentadecine shows this to be meso-dimethyl isomer. Condensation of 2,2 '-(oxalyldiimino)bisbenzophenone with diamines in the presence of copper(ll) acetate yields macrocyclic neutral copper(ll) complexes which contain a dioxo linkage between the anilino nitrogen atoms. An X-ray structure determination of [5,12-diphenyl-18,19-dioxo-9,10,17,18,19,20-hexahydrodibenzo (e,m) (1,4,8,11) tetraazacyclotetradecinato(2-)]-dimethylformamidocopper II dihydrate indicates steric crowding for the phenyl substituents on the imine carbon atoms. Polycyclic tetraza compounds result from the condensation of the cyclic tetraamines with glyoxal.
A group of 20,21 and 22-membered sexadentate ligands having N402 donor sets, and 20-membered ligands with N4S2 and N6 donor sets have also been studied; e.g.: 12,13,25,26,27,28-Hexahydrotetrabenzo (e,i,o,s) (11,14,1,4,8,17) dithiatetraazacycloeicosine. Reduction of the azomethine linkages was achieved for all these ligands and cationic copper(ll) complexes have been prepared and characterised. An X-ray structure determination showed that one of the N402 tetraamine ligands uses only three of its nitrogen atoms in forming a complex with copper(II).
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