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 | |
| Publication status | Published - 2000 Jun 12 |
| Externally published | Yes |
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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 journal › Article
}
TY - JOUR
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
Y1 - 2000/6/12
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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U2 - 10.1021/ic991404z
DO - 10.1021/ic991404z
M3 - Article
VL - 39
SP - 2696
EP - 2698
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 12
ER -