Electrocatalytic water oxidation activity of a copper(ii) complex, 1, [Cu(L1H)(L1)(OH2)](ClO4), with a redox active aryl oxime ligand, L1H [L1H = 1-(pyridin-2-yl) ethanone oxime] has been investigated.
The reaction of a Cu(II)-nitrosyl complex (1) with hydrogen peroxide at -20 °C in acetonitrile results in the formation of the corresponding Cu(I)-peroxynitrite intermediate. The reduction of the Cu(II) center was monitored by UV-visible spectroscopic studies. Formation of the peroxynitrite intermediate has been confirmed by its characteristic phenol ring nitration reaction as well as isolation of corresponding Cu(I)-nitrate (2). On air oxidation, 2 resulted in the corresponding Cu(II)-nitrate (3). Thus, these results demonstrate a possible decomposition pathway for H(2)O(2) and NO through the formation of a peroxynitrite intermediate in biological systems.
The quenched fluorescent intensity of a copper(II) complex, 1, of a fluorescent ligand, in degassed methanol or aqueous (buffered at pH 7.2) solution, was found to reappear on exposure to nitric oxide. Thus, it can function as a fluorescence based nitric oxide sensor. It has been found that the present complex can be used to sense nanomolar quantities of nitric oxide in both methanol and pH 7.2 buffered-water medium.
The copper(II) centers in two copper(II) complexes of tripodal amine ligands, in acetonitrile solvent, upon exposure to nitric oxide have been found to produce a thermally unstable [Cu(II)-NO] intermediate followed by the reduction of copper(II) to copper(I). This reduction resulted in the concomitant trinitrosation of the ligands at their terminal amine centers.
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