Electron Transfer Mechanism of Organocobalt Porphyrins. Site of Electron Transfer, Migration of Organic Groups, and Cobalt−Carbon Bond Energies in Different Oxidation States

DOI Web Site 被引用文献4件
  • Shunichi Fukuzumi
    Contribution from the Department of Applied Chemistry, Faculty of Engineering, Osaka University, Osaka 565-0871, Japan, and Department of Chemistry, University of Houston, Houston, Texas 77204-5641
  • Kenichi Miyamoto
    Contribution from the Department of Applied Chemistry, Faculty of Engineering, Osaka University, Osaka 565-0871, Japan, and Department of Chemistry, University of Houston, Houston, Texas 77204-5641
  • Tomoyoshi Suenobu
    Contribution from the Department of Applied Chemistry, Faculty of Engineering, Osaka University, Osaka 565-0871, Japan, and Department of Chemistry, University of Houston, Houston, Texas 77204-5641
  • Eric Van Caemelbecke
    Contribution from the Department of Applied Chemistry, Faculty of Engineering, Osaka University, Osaka 565-0871, Japan, and Department of Chemistry, University of Houston, Houston, Texas 77204-5641
  • Karl M. Kadish
    Contribution from the Department of Applied Chemistry, Faculty of Engineering, Osaka University, Osaka 565-0871, Japan, and Department of Chemistry, University of Houston, Houston, Texas 77204-5641

書誌事項

公開日
1998-03-11
DOI
  • 10.1021/ja973257e
公開者
American Chemical Society (ACS)

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説明

The chemical or electrochemical oxidations and coupled chemical reactions of (TPP)Co(R) and (TPP)Co(R)(L) where R = Bu, Et, Me, or Ph, L = a substituted pyridine, and TPP = the dianion of tetraphenylporphyrin were investigated in acetonitrile or dichloromethane. The homogeneous one- or two-electron oxidation of the Co(III) σ-bonded complexes was accomplished using [Fe(phen)3]3+ (phen = 1,10-phenanthroline) as an oxidant. The products of the initial oxidation as well as that of the subsequent R group migration from (TPP)Co(R) or (TPP)Co(R)(L) to give the N-aryl or N-alkyl Co(II) porphyrins were characterized by ESR and UV−vis spectroscopies, while the rates of migration were determined using stopped flow kinetics. The rate constants of R group migration from the metal to nitrogen in [(TPP)Co(R)]+ were found to vary by 6 orders of magnitude upon going from (TPP)Co(Ph) (1.3 × 10-3 s-1) to (TPP)Co(Bu) (1.2 × 103 s-1) at 298 K in acetonitrile, but no significant differences were observed between E1/2 for the f...

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