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Increased valence theory and the four electron reduction of O2 to H2O

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  • Chemistry


PII: 0166-1280(88)80097-6 Journal of Molecular Structure (Theochem), 186 (1988) 309-318 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands 309 INCREASED VALENCE THEORY AND THE FOUR ELECTRON REDUCTION OF O2 TO Hz0 A. VAN DER PUTTEN, A. ELZING, W. VISSCHER and E. BARENDRECHT Laboratory for Electrochemistry, Department of Chemical Technology, Eindhoven University of Technology, P.O. Box 513,560O MB Eindhoven (The Netherlands) R.D. HARCOURT Department of Physical Chemistry, University of Melbourne, Parkville, Victoria 3052 (Australia) (Received 23 November 1987) ABSTRACT The four electron reduction of oxygen to water, without the intermediate formation of hydrogen peroxide has been reported on dicofacial dicobalt porphyrins and planar dicobaltchelates, con- taining two CON, units in the plane of the molecules. These two classes of compounds display “reversed selectivity” with respect to the solution pH. Dicofacial dicobalt porphyrins directly reduce O2 to Hz0 in acid solution, and to hydrogen peroxide in alkaline solution. Planar dico- baltchelates show four electron reduction of 0, in alkaline solution, but yield exclusively hydrogen peroxide at low pH. By using the increased valence theory, an attempt is made to provide a valence bond repreeen- tation for the electronic reorganization that could be associated with each of these phenomena. For the results obtained in acid solution, this theory indeed offers an excellent description. In alkaline solution, however, application of the increasedvalence theory alone does not fully account for the experimental observations, unless the following condition is also satisfied. Besides bridge adsorption of oxygen, appropriate values for the redox potentials of the Co centres also seem to be a prerequisite for the occurrence of direct reduction of oxygen to water. INTRODUCTION The electrochemical reduction of 0, has been extensively studied [ 11, not only for a better understanding of

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