Mixed ruthenium-rhodium trinuclear complex [Ru2Rh(μ3-O)(μ-CH3COO) 6(L)3]+ (L = H2O or pyridine)

Yoichi Sasaki, Ayako Yamamoto, Tasuku Ito

Research output: Contribution to journalArticle

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Abstract

The preparation and purification method of a new ruthenium(III)-rhodium(III) cluster, [Ru2Rh(μ3-O) (μ-CH3COO)6(L)3]+ (L = H2O or pyridine (py)), are described. The mixed-metal structure was confirmed by the 1H and 13C NMR spectra (splitting of all the signals to a 1:2 intensity ratio) and the metal 3d electron signal intensities of the X-ray photoelectron spectra. The mixed-metal aqua and pyridine complexes exhibit an intense visible absorption peak at 576 nm (ε 2000 M-1 cm-1) and 590 (3980), respectively. Three reversible one-electron-redox waves are observed at +1.68, +0.79, and -0.78 V vs the Ag/Ag+ electrode for the pyridine complex in CH3CN and are assigned to [Ru2Rh]3+/2+, [Ru2Rh]2+/+, and [Ru2Rh]+/0, respectively. The 1H NMR spectrum of the aqua complex in CD3OD changes slowly as the substitution of CD3OD for the aqua ligands takes place, first-order rate constants being 6.0 × 10-5 (per Ru) and 1.2 × 10-4s-1 at the ruthenium and the rhodium centers, respectively, at 21°C.

Original languageEnglish
Pages (from-to)6341-6347
Number of pages7
JournalJournal of the American Chemical Society
Volume109
Issue number21
Publication statusPublished - 1987
Externally publishedYes

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Rhodium
Ruthenium
Pyridine
Metals
Nuclear magnetic resonance
Electrons
Photoelectrons
Purification
Rate constants
Substitution reactions
Ligands
X rays
Electrodes
pyridine

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Mixed ruthenium-rhodium trinuclear complex [Ru2Rh(μ3-O)(μ-CH3COO) 6(L)3]+ (L = H2O or pyridine). / Sasaki, Yoichi; Yamamoto, Ayako; Ito, Tasuku.

In: Journal of the American Chemical Society, Vol. 109, No. 21, 1987, p. 6341-6347.

Research output: Contribution to journalArticle

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abstract = "The preparation and purification method of a new ruthenium(III)-rhodium(III) cluster, [Ru2Rh(μ3-O) (μ-CH3COO)6(L)3]+ (L = H2O or pyridine (py)), are described. The mixed-metal structure was confirmed by the 1H and 13C NMR spectra (splitting of all the signals to a 1:2 intensity ratio) and the metal 3d electron signal intensities of the X-ray photoelectron spectra. The mixed-metal aqua and pyridine complexes exhibit an intense visible absorption peak at 576 nm (ε 2000 M-1 cm-1) and 590 (3980), respectively. Three reversible one-electron-redox waves are observed at +1.68, +0.79, and -0.78 V vs the Ag/Ag+ electrode for the pyridine complex in CH3CN and are assigned to [Ru2Rh]3+/2+, [Ru2Rh]2+/+, and [Ru2Rh]+/0, respectively. The 1H NMR spectrum of the aqua complex in CD3OD changes slowly as the substitution of CD3OD for the aqua ligands takes place, first-order rate constants being 6.0 × 10-5 (per Ru) and 1.2 × 10-4s-1 at the ruthenium and the rhodium centers, respectively, at 21°C.",
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AU - Ito, Tasuku

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