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

doi:10.1021/ic991404z

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 journal › Article › peer-review

25 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	2696-2698
Number of pages	3
Journal	Inorganic Chemistry
Volume	39
Issue number	12
DOIs	https://doi.org/10.1021/ic991404z
Publication status	Published - 2000 Jun 12
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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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 journal › Article › peer-review

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

abstract = "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.",

author = "Zavarine, {Igor S.} and Kubiak, {Clifford P.} and Tadashi Yamaguchi and Ota, {Ken Ichiro} and Taeko Matsui and Tasuku Ito",

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T1 - Unusual redox state dependent fermi resonances in the infrared spectra of trinuclear ruthenium clusters with isocyanide ligands

AU - Zavarine, Igor S.

AU - Kubiak, Clifford P.

AU - Yamaguchi, Tadashi

AU - Ota, Ken Ichiro

AU - Matsui, Taeko

AU - Ito, Tasuku

PY - 2000/6/12

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N2 - 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.

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

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