Electron transfer from tetrakis(isocyanide)rhodium(I) monomers, and the oligomers to iron(III) and cobalt(III) complexes. Enhancement of the reactivity by the oligomerization.
スポンサーリンク
概要
- 論文の詳細を見る
Electron transfer reactions from tetrakis(isocyanide)rhodium(I) ([RhL<SUB>4</SUB>]<SUP>+</SUP> to iron(III) complexes of the [Fe(N–N)<SUB>3</SUB>]<SUP>3+</SUP> type (N–N=1,10-phenanthroline, 2,2′-bipyridine) proceed through precursor complexes formed between [RhL<SUB>4</SUB>]<SUP>+</SUP> and [Fe(N–N)<SUB>3</SUB>]<SUP>3+</SUP> with 1:1, 1:2, and 2:1 stoichiometry. A similar scheme is suggested for the reaction of bis(isocyanide)bis(triphenylphosphine)rhodium(I) with the same oxidants. The intramolecular electron transfer rate constants <I>k</I><SUB>1</SUB> in the 1:1 precursor complexes have been determined in MeCN at 298 K. In accordance with Marcus theory, the log<I>k</I><SUB>1</SUB> values are linearly related with the reduction potentials of oxidants with the theoretical slope of 8.5. The [RhL<SUB>4</SUB>]<SUP>+</SUP> cations form oligomers in MeCN; [RhL<SUB>4</SUB><SUP>+</SUP>]<I><SUB>n</SUB></I> (<I>n</I>=2,3), and the equilibrium constants for oligomerization have been determined. For a given oxidant [Co(bpy)<SUB>3</SUB>]<SUP>3+</SUP> (bpy=2,2′-bipyridine), the log<I>k</I><SUB>1</SUB> value of [RhL<SUB>4</SUB><SUP>+</SUP>]<I><SUB>n</SUB></I> increases in parallel with the HOMO energy of [RhL<SUB>4</SUB><SUP>+</SUP>]<I><SUB>n</SUB></I>; monomer<dimer<trimer.
- 公益社団法人 日本化学会の論文
著者
-
Fukuzumi Shunichi
Department Of Applied Chemistry Faculty Of Engineering Osaka University
-
Tanaka Toshio
Department of Applied Chemistry, Faculty of Engineering, Osaka Univeristy
-
Nishizawa Nobuaki
Department of Applied Chemistry, Faculty of Engineering, Osaka University
関連論文
- Scandium Ion-accelerated Scavenging Reaction of Cumylperoxyl Radical by a Cyclic Nitroxyl Radical via Electron Transfer
- Involvement of Electron Transfer in the Radical-scavenging Reaction of Resveratrol
- Effect of Solvent Polarity on the One-electron Oxidation of Cyclic Nitroxyl Radicals
- EPR Study on Stable Magnesium Complexes of the Phenoxyl Radicals Derived from a Vitamin E Model and Its Deuterated Derivatives
- Elastic Stiffness Constants of Cadmium Sulfide
- Imatinib mesylate inhibited rat adjuvant arthritis and PDGF-dependent growth of synovial fibroblast via interference with the Akt signaling pathway
- Preventative Effect of a Flavonoid, Enzymatically Modified Isoquercitrin on Ocular Symptoms of Japanese Cedar Pollinosis
- Flavonoids and Related Compounds as Anti-Allergic Substances
- Vegetarian Diet Ameliorates Symptoms of Atopic Dermatitis through Reduction of the Number of Peripheral Eosinophils and of PGE2 Synthesis by Monocytes
- Quantitative Evaluation of Lewis Acidity of Organotin Compounds and the Catalytic Reactivity in Electron Transfer