Synthesis and properties of the cyano complex of oxo-centered triruthenium core [Ru33-O)(μ-CH3COO) 6(pyridine)2(CN)]

Hua Xin Zhang, Yoichi Sasaki, Yi Zhang, Shen Ye, Masatoshi Osawa, Masaaki Abe, Kohei Uosaki

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13 Citations (Scopus)


The preparation and properties of a new cyano complex containing the Ru33-O) core, [Ru33-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 33-O)(μ-CH3COO)6(py) 3]+. This is in sharp contrast to the positive shifts of the corresponding waves of [Ru3 II,III,III3-O)(μ-CH3COO) 6(py)2(CO)]. Density functional theory (DFT) calculations of [Ru3II,III,III3-O)(μ-CH 3COO)6(py)3], [Ru3 II,III,III3-O)(μ-CH3COO) 6(py)2(CN)]-, and [Ru3 II,III,III3-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.

Original languageEnglish
Pages (from-to)1288-1294
Number of pages7
JournalInorganic Chemistry
Issue number3
Publication statusPublished - 2014 Feb 3


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