ESR Spectra of six-coordinate cobalt(III) tetraphenylporphyrin cation radicals generated by electrochemical oxidation.

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概要

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• The ESR spectra of the paramagnetic species generated electrochemically from α,β,γ,δ-tetraphenylporphinatocobalt(II), [Co<SUP>II</SUP>(tpp)], have been observed under the conditions of low-temperature, in chlorinated or nonchlorinated solvents, and in the presence of various supporting electrolytes. From the ESR parameters obtained, three different paramagnetic species, [Co<SUP>III</SUP>(tpp)]<SUP>2+</SUP>(X<SUP>−</SUP>)<SUB>2</SUB>, [Co<SUP>III</SUP>(tpp)]<SUP>2+</SUP>(Y<SUP>−</SUP>)<SUB>2</SUB>, and [Co<SUP>III</SUP>(tpp)]<SUP>2+</SUP>(X<SUP>−</SUP>)(Y<SUP>−</SUP>), have been confirmed. The ESR spectrum of thermally and optically accessible paramagnetic species in the solution of chlorotetraphenylporphinatocobalt(III) has been reproduced by the pertinent combination of solvent and supporting electrolyte, and well interpreted by assuming the formation of [Co<SUP>III</SUP>(tpp)]<SUP>2+</SUP>(Cl<SUP>−</SUP>)<SUB>2</SUB>. Arguing from a correlation between the hfcc of cobalt and nitrogen nuclei in this species, a spin-polarization mechanism is proposed to interpret the cobalt hfcc.

• 公益社団法人 日本化学会の論文

著者

• Yamamoto Kiyoko

  The Institute of Physical and Chemical Research

• Ohya-Nishiguchi Hiroaki

  Department of Chemistry, Faculty of Science, Kyoto University

• Khono Masahiro

  JEOL Ltd.

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