Unusual redox state dependent fermi resonances in the infrared spectra of trinuclear ruthenium clusters with isocyanide ligands

Igor S. Zavarine, Clifford P. Kubiak, Tadashi Yamaguchi, Ken Ichiro Ota, Taeko Matsui, Tasuku Ito

Research output: Contribution to journalArticle

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Abstract

Four different redox states of the trinuclear ruthenium clusters of general formula [Ru33-O)(μ-CH3CO2)6(L)3] (L = xylyl isocyanide (1), tert-butyl isocyanide (2)) were generated electrochemically in solution and studied by reflectance infrared spectroelectrochemistry. The IR spectra in the v-(C≡N) region show multiple-band structure in the Ru(III)Ru(II)2 ( - 1) and uRu(III)2Ru(II) (0) states but a sharp single band in the Ru(III)3 (+1) or Ru(IV)Ru(III)2 (+2) state. Density functional theory (DFT) ab initio calculations were performed for free xylyl isocyanide and tert-butyl isocyanide. The results suggest that the C≡N - C bending mode interacts through Fermi resonance with the v(C≡N) fundamental for the 0 and - 1 states of both 1 and 2. The extensive redox chemistry of the Ru3-(μ3-O) clusters 1 and 2 offers a convenient means of effecting shifts in the energy of v(C≡N) bands of coordinated isocyanide ligands, in and out of Fermi resonance with the C≡N - C bending overtone.

Original languageEnglish
Pages (from-to)2696-2698
Number of pages3
JournalInorganic Chemistry
Volume39
Issue number12
DOIs
Publication statusPublished - 2000 Jun 12
Externally publishedYes

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Ruthenium
Cyanides
ruthenium
infrared spectra
Spectroelectrochemistry
Ligands
Infrared radiation
ligands
Band structure
Density functional theory
chemistry
density functional theory
reflectance
harmonics
shift
Oxidation-Reduction
tert-butyl isocyanide
energy

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Unusual redox state dependent fermi resonances in the infrared spectra of trinuclear ruthenium clusters with isocyanide ligands. / Zavarine, Igor S.; Kubiak, Clifford P.; Yamaguchi, Tadashi; Ota, Ken Ichiro; Matsui, Taeko; Ito, Tasuku.

In: Inorganic Chemistry, Vol. 39, No. 12, 12.06.2000, p. 2696-2698.

Research output: Contribution to journalArticle

Zavarine, Igor S. ; Kubiak, Clifford P. ; Yamaguchi, Tadashi ; Ota, Ken Ichiro ; Matsui, Taeko ; Ito, Tasuku. / Unusual redox state dependent fermi resonances in the infrared spectra of trinuclear ruthenium clusters with isocyanide ligands. In: Inorganic Chemistry. 2000 ; Vol. 39, No. 12. pp. 2696-2698.
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AB - Four different redox states of the trinuclear ruthenium clusters of general formula [Ru3(μ3-O)(μ-CH3CO2)6(L)3] (L = xylyl isocyanide (1), tert-butyl isocyanide (2)) were generated electrochemically in solution and studied by reflectance infrared spectroelectrochemistry. The IR spectra in the v-(C≡N) region show multiple-band structure in the Ru(III)Ru(II)2 ( - 1) and uRu(III)2Ru(II) (0) states but a sharp single band in the Ru(III)3 (+1) or Ru(IV)Ru(III)2 (+2) state. Density functional theory (DFT) ab initio calculations were performed for free xylyl isocyanide and tert-butyl isocyanide. The results suggest that the C≡N - C bending mode interacts through Fermi resonance with the v(C≡N) fundamental for the 0 and - 1 states of both 1 and 2. The extensive redox chemistry of the Ru3-(μ3-O) clusters 1 and 2 offers a convenient means of effecting shifts in the energy of v(C≡N) bands of coordinated isocyanide ligands, in and out of Fermi resonance with the C≡N - C bending overtone.

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