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

^*Corresponding author for this work

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

26 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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