Preparation and physicochemical properties of new linear .MU.-oxo bridged ruthenium(IV) and osmium(IV) porphyrin dimers.

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概要

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• μ-Oxo-bis[(hydroxo)(octaethylporphyrinato)ruthenium(IV)] was prepared by the oxidation of (carbonyl)(octaethylporphyrinato)ruthenium(II) with <I>t</I>-butyl hydroperoxide in good yield. Facile replacement of the hydroxyl group with various anions afforded μ-oxo dimer complexes formulated as [{Ru<SUP>IV</SUP>(oep)X}<SUB>2</SUB>O] (X=Cl, Br, and OCOCH<SUB>3</SUB>). The same type of osmium complexes, [{Os<SUP>IV</SUP>(oep)(OCH<SUB>3</SUB>)}O], {[Os<SUP>IV</SUP>(oep)(OCH<SUB>3</SUB>)}O{Os<SUP>IV</SUP>(oep)(OH)}], and [{Os<SUP>IV</SUP>(oep)(OH)}<SUB>2</SUB>O] were obtained from the air oxidation product of (carbonyl)(methanol)(octaethylporphyrinato)osmium(II) in the presence of 2,3-dimethylindole. These complexes are diamagnetic. The <SUP>1</SUP>H NMR data are in conformity with the linear oxo-bridged dimer structure which was proved by X-ray crystallography with [{Ru<SUP>IV</SUP>(oep)(OH)}<SUB>2</SUB>O]. The redox potentials were measured by the cyclic voltammetry. These complexes showed three distinct quasi-reversible redox couples assignable to metal<SUP>II</SUP>/ metal<SUP>III</SUP>, metal<SUP>III</SUP>/metal<SUP>IV</SUP>, and porphyrin ligand oxidation, respectively. Significantly lower redox values and anomalous spectral features indicate a strong pπ-dπ interaction between the bridging oxygen atom and the two quadrivalent metal ions.

• 公益社団法人 日本化学会の論文

著者

• Higashi Teruaki

  Department Of Biology Faculty Of Science Yamaguchi University

• Yoshida Zen-ichi

  Department Of Applied Chemistry Faculty Of Science And Engineering Kinki University

• Sugimoto Hiroshi

  Department Of Aeronautics And Astronautics Graduate School Of Engineering Kyoto University

• OGOSHI Hisanobu

  Department of Chemistry, Faculty of Engineering, Technical University of Nagaoka

• Mori Masayasu

  Department of Chemistry, Faculty of Science, Osaka City University

• Nagano Motoi

  Department of Synthetic Chemistry, Faculty of Engineering, Kyoto University

• Higashi Teruaki

  Department of Chemistry, Faculty of Science, Osaka City University

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