Theoretical study of the electron transfer reaction of hydrazine with cobalt(II) phthalocyanine and substituted cobalt(II) phthalocyanines

Author: Venegas-Yazigi Diego A.   Cárdenas-Jirón Gloria I.   Zagal José H.  

Publisher: Taylor & Francis Ltd

ISSN: 0095-8972

Source: Journal of Coordination Chemistry, Vol.56, Iss.14, 2003-09, pp. : 1269-1275

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Abstract

A theoretical model is proposed to explain the trend in reactivity of cobalt(II) phthalocyanine (CoPc) and substituted cobalt(II) phthalocyanines for the oxidation of hydrazine. Our study suggests that the reaction occurs via a through bond charge transfer pathway and not via a through space charge transfer pathway as was shown in previous work for the oxidation of 2-mercaptoethanol by CoPc (G.I. Cárdenas-Jirón and D.A. Venegas-Yazigi, J. Phys. Chem. A. 106, 11398 (2002)). We propose a mechanism for the oxidation of hydrazine based on a four-step energy profile which agrees with a mechanism proposed for the electro-oxidation of hydrazine mediated by cobalt phthalocyanines confined on a graphite electrode. We show that the step in the energy profile that involves formation of a radical of hydrazine seems to be a good starting point for the study of the transfer of the first electron in the oxidation of hydrazine mediated by different substituted cobalt(II) phthalocyanines.