Synthesis and Properties of the Cyano Complex of Oxo-Centered Triruthenium Core [Ru<sub>3</sub>(μ<sub>3</sub>-O)(μ-CH<sub>3</sub>COO)<sub>6</sub>(pyridine)<sub>2</sub>(CN)]
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- Hua-Xin Zhang
- Catalysis Research Center, Hokkaido University, Sapporo 001-0021, Japan
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- Yoichi Sasaki
- Catalysis Research Center, Hokkaido University, Sapporo 001-0021, Japan
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- Yi Zhang
- Catalysis Research Center, Hokkaido University, Sapporo 001-0021, Japan
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- Shen Ye
- Catalysis Research Center, Hokkaido University, Sapporo 001-0021, Japan
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- Masatoshi Osawa
- Catalysis Research Center, Hokkaido University, Sapporo 001-0021, Japan
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- Masaaki Abe
- Department of Applied Chemistry, Graduate School of Engineering, Kyushu University, Nishi-ku, Fukuoka 819-0395, Japan
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- Kohei Uosaki
- Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan
書誌事項
- 公開日
- 2013-12-05
- 資源種別
- journal article
- DOI
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- 10.1021/ic4012197
- 公開者
- American Chemical Society (ACS)
この論文をさがす
説明
The preparation and properties of a new cyano complex containing the Ru3(μ3-O) core, [Ru3(μ3-O)(μ-CH3COO)6(py)2(CN)] (1; py = pyridine), are reported. Complex 1 in CH2Cl2 showed intense absorption bands at 244, 334, and 662 nm, corresponding to a π-π* transition of the ligand, cluster-to-ligand charge transfer, and intracluster transitions, respectively. The cyclic voltammogram of 1 in 0.1 M (n-Bu)4NPF6-CH2Cl2 showed redox waves for the processes Ru3(II,II,III)/Ru3(II,III,III), Ru3(II,III,III)/Ru3(III,III,III), and Ru3(III,III,III)/Ru3(III,III,IV) at E1/2 = -1.49, -0.26, and +1.03 V vs Ag/AgCl, respectively. The first two redox potentials are more negative by ca. 0.2 V in comparison with the corresponding potentials of [Ru3(μ3-O)(μ-CH3COO)6(py)3](+). This is in sharp contrast to the positive shifts of the corresponding waves of [Ru3(II,III,III)(μ3-O)(μ-CH3COO)6(py)2(CO)]. Density functional theory (DFT) calculations of [Ru3(II,III,III)(μ3-O)(μ-CH3COO)6(py)3], [Ru3(II,III,III)(μ3-O)(μ-CH3COO)6(py)2(CN)](-), and [Ru3(II,III,III)(μ3-O)(μ-CH3COO)6(py)2(CO)] showed that the positive charge of the ruthenium is delocalized over the triruthenium cores of the first two and is localized as Ru(II)(CO){Ru(III)(py)}2 in the CO complex. The calculations explain the difference in the π interactions of the two ligands with the triruthenium cores.
収録刊行物
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- Inorganic Chemistry
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Inorganic Chemistry 53 (3), 1288-1294, 2013-12-05
American Chemical Society (ACS)