TY - JOUR
T1 - Synthesis and properties of the cyano complex of oxo-centered triruthenium core [Ru3(μ3-O)(μ-CH3COO) 6(pyridine)2(CN)]
AU - Zhang, Hua Xin
AU - Sasaki, Yoichi
AU - Zhang, Yi
AU - Ye, Shen
AU - Osawa, Masatoshi
AU - Abe, Masaaki
AU - Uosaki, Kohei
PY - 2014/2/3
Y1 - 2014/2/3
N2 - 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 Ru3II,II,III/Ru3 II,III,III, Ru3II,III,III/Ru3 III,III,III, and Ru3III,III,III/Ru 3III,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 [Ru 3(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 [Ru3II,III,III(μ3-O)(μ-CH 3COO)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 RuII(CO){RuIII(py)}2 in the CO complex. The calculations explain the difference in the π interactions of the two ligands with the triruthenium cores.
AB - 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 Ru3II,II,III/Ru3 II,III,III, Ru3II,III,III/Ru3 III,III,III, and Ru3III,III,III/Ru 3III,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 [Ru 3(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 [Ru3II,III,III(μ3-O)(μ-CH 3COO)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 RuII(CO){RuIII(py)}2 in the CO complex. The calculations explain the difference in the π interactions of the two ligands with the triruthenium cores.
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U2 - 10.1021/ic4012197
DO - 10.1021/ic4012197
M3 - Article
C2 - 24304468
AN - SCOPUS:84893222737
SN - 0020-1669
VL - 53
SP - 1288
EP - 1294
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 3
ER -