Abstract
Sublimed films ofmeso-tetraphenylporphyrinatocobalt(II) (CoTPP) undergo a series of chemical transformations in an atmosphere of NO2. In the first stage, at low NO2 pressures, the axial five-coordinate CoIIITPP·NO2 complex is formed. An increase in the NO2 pressure and/or exposure results in subsequent oxidation with the formation of a π-radical cation CoTPP.+. In the latter, according to the IR spectral data, nitrogen dioxide is axially coordinated by the cobalt ion. Further increase in the NO2 pressure leads to both the formation of a dication and nitration of the porphyrin ring most likely at themeso- and β-pyrrolic positions. Irreversible chemical transformations in the sublimed CoTPP films prevent their use as NO2 sensors.
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 716–719, April, 1998.
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Kurtikyan, T.S., Stepanyan, T.G. Oxidation sequence of sublimedmeso-tetraphenylporphyrinatocobalt(II) films in an atmosphere of nitrogen dioxide. Russ Chem Bull 47, 695–698 (1998). https://doi.org/10.1007/BF02495982
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DOI: https://doi.org/10.1007/BF02495982