Tetraazamacrocyclic ligands and their copper complexes

Judd, P. M. (1982) Tetraazamacrocyclic ligands and their copper complexes. Doctoral thesis, Polytechnic of North London.

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Abstract / Description

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).

Item Type: Thesis (Doctoral)
Additional Information: uk.bl.ethos.331130
Subjects: 500 Natural Sciences and Mathematics > 540 Chemistry & allied sciences
Department: School of Human Sciences
Depositing User: Maria White
Date Deposited: 03 Oct 2018 15:23
Last Modified: 03 Oct 2018 15:23
URI: http://repository.londonmet.ac.uk/id/eprint/3444

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