Mixed Ruthenium-rhodium Trinuclear Complex [Ru2Rh(m3-oo)(ai-CH3COO)6(L)3]+(L = H2O or Pyridine)

Yoichi Sasaki; Ayako Tokiwa; Tasuku Ito

doi:10.1021/ja00255a018

Mixed Ruthenium-rhodium Trinuclear Complex [Ru₂Rh(m₃-oo)(ai-CH₃COO)₆(L)3]⁺(L = H₂O or Pyridine)

Yoichi Sasaki, Ayako Tokiwa, Tasuku Ito

Research output: Contribution to journal › Article › peer-review

62 Citations (Scopus)

Abstract

The preparation and purification method of a new ruthenium(III)-rhodium(III) cluster, [Ru₂Rh(u₃-0)(u-CH₃COO)₆(L)₃]⁺(L = H₂0 or pyridine (py)), are described. The mixed-metal structure was confirmed by the¹H and¹³C 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 (e 2000 M^-1cm^-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^lH 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 X 10^-5(per Ru) and 1.2 X 10^-4s^-1at the ruthenium and the rhodium centers, respectively, at 21 °C.

Original language	English
Pages (from-to)	6341-6347
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	109
Issue number	21
DOIs	https://doi.org/10.1021/ja00255a018
Publication status	Published - 1987 Oct 1
Externally published	Yes

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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title = "Mixed Ruthenium-rhodium Trinuclear Complex [Ru2Rh(m3-oo)(ai-CH3COO)6(L)3]+(L = H2O or Pyridine)",

abstract = "The preparation and purification method of a new ruthenium(III)-rhodium(III) cluster, [Ru2Rh(u3-0)(u-CH3COO)6(L)3]+(L = H20 or pyridine (py)), are described. The mixed-metal structure was confirmed by the1H and13C 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 (e 2000 M-1cm-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. ThelH 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 X 10-5(per Ru) and 1.2 X 10-4s-1at the ruthenium and the rhodium centers, respectively, at 21 °C.",

author = "Yoichi Sasaki and Ayako Tokiwa and Tasuku Ito",

year = "1987",

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doi = "10.1021/ja00255a018",

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T1 - Mixed Ruthenium-rhodium Trinuclear Complex [Ru2Rh(m3-oo)(ai-CH3COO)6(L)3]+(L = H2O or Pyridine)

AU - Sasaki, Yoichi

AU - Tokiwa, Ayako

AU - Ito, Tasuku

PY - 1987/10/1

Y1 - 1987/10/1

N2 - The preparation and purification method of a new ruthenium(III)-rhodium(III) cluster, [Ru2Rh(u3-0)(u-CH3COO)6(L)3]+(L = H20 or pyridine (py)), are described. The mixed-metal structure was confirmed by the1H and13C 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 (e 2000 M-1cm-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. ThelH 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 X 10-5(per Ru) and 1.2 X 10-4s-1at the ruthenium and the rhodium centers, respectively, at 21 °C.

AB - The preparation and purification method of a new ruthenium(III)-rhodium(III) cluster, [Ru2Rh(u3-0)(u-CH3COO)6(L)3]+(L = H20 or pyridine (py)), are described. The mixed-metal structure was confirmed by the1H and13C 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 (e 2000 M-1cm-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. ThelH 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 X 10-5(per Ru) and 1.2 X 10-4s-1at the ruthenium and the rhodium centers, respectively, at 21 °C.

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Mixed Ruthenium-rhodium Trinuclear Complex [Ru₂Rh(m₃-oo)(ai-CH₃COO)₆(L)3]⁺(L = H₂O or Pyridine)

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