Year

1992

Degree Name

Doctor of Philosophy

Department

Department of Chemistry

Abstract

Thirty two binuclear copper (II) complexes based on 1,3-bis(salicylaldimino)propan-2-ol (SAL-DPLH3), 1,5-bis(salicylaldimino)pentan-3-ol (SAL-DPEH3) and 1,3-bis (4,5'-dimcihyl-2-hydroxybenzophenimino)propan-2-ol (M2BP-DPLH3) have been prepared as models of the suucturc of the Type III copper centre of Tyrosinase. A further four complexes (one mononuclear and three pentanuclear complexes) based on the above ligands were prepared and added to the thirty two compounds in a study of models of the electrochemical activity of the Type II and Type III copper centres of multicopper oxidases. A new synthetic method was developed using Cu(XSAL)2 as the copper source.

A series of binuclear copper (II) complexes with a catechol exogenous bridge were synthesised. The infra-red spectra, visible spectra, mass spectra, magnetism and electrochemistry of these complexes were measured. The crystal structures of "Cu2(SAL-DPL)NH2O", Cu2(SAL-DPL)6-AI and Cu2(M2BP-DPL)M2Pz were obtained.

The complexes were found to undergo reduction from copper (II) to copper metal in DMF solutions against a variety of electrodes with the electrode material being a mercury pool, dropping mercury, hanging mercury drop, platinum and glassy carbon. Coulometry, polarography, differential pulse voltammetry and cyclic voltammetry were used to elucidate the electrochemistry of these complexes. The complexes all were reduced in the range 0 to -2000mV. Some of these complexes were found to have quasi-reversible redox properties and the rest were found to have irreversible redox properties.

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Unless otherwise indicated, the views expressed in this thesis are those of the author and do not necessarily represent the views of the University of Wollongong.