Abstract
This thesis deals with various aspects of the chemistry of metal complexes with amino acid derivatives and related ligands. The introduction covers background literature on these complexes particularly in relation to their reactions in solution. A number of copper(II) and nickel(II) complexes of the ligand 2-(2'-acetoxyethylamino)ethylamine, NH2 (CH2)2)NH(CH2)2 OCOCH3, have been synthesised and characterised by spectroscopic and magnetic measurements. The complexes isolated depend on whether or not the non-complexing base, triethylamine, is added to the reaction mixture, which contains the ligand (L) as the dihydrochloride or dihydrobromide. Hence complexes such as LH2 [CuBr4] or CuLBr2 may be obtained, depending on the conditions. The tetramethylamide of EDTA has been synthesised and its complexes with a number of metal ions (e.g. Cu(II), Ni(II), Co(II), Zn(II), Fe(III), Cd(II)) have been isolated. In these complexes the ligand is either a tetradentate 2N,2O donor or a hexadentate 2N,4O donor. The metal ion promoted hydrolysis of diimides of EDTA and related compound are also described. In particular the hydrolysis of 1,2-bis(3,5-dioxopiperazin-1-yl)propane in the presence of copper(II) has been investigated in detail. This compound is anticancer drug, razoxane, and its activity is due to the fact that it is metabolised in vivo to a chelating agent which interferes with metalloenzymes necessary for the growth of tumour cells. In the copper(II) promoted hydrolysis of razoxane only one of the imide rings is opened but this produces a chelating agent which, based on its structure, should strongly bind metal ions.