Synthesis and Properties of the Cyano Complex of Oxo-Centered Triruthenium Core [Ru3(μ3-O)(μ-CH3COO)6(pyridine)2(CN)]

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• 作者：Hua-Xin Zhang ; Yoichi Sasaki ; Yi Zhang ; Shen Ye ; Masatoshi Osawa ; Masaaki Abe ; Kohei Uosaki
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：February 3, 2014
• 年：2014
• 卷：53
• 期：3
• 页码：1288-1294
• 全文大小：363K
• ISSN：1520-510X

文摘

The preparation and properties of a new cyano complex containing the Ru₃(渭₃-O) core, [Ru₃(渭₃-O)(渭-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 蟺鈥撓€* 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鈥揅H₂Cl₂ 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 E_1/2 = 鈭?.49, 鈭?.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(渭₃-O)(渭-CH₃COO)₆(py)₃]⁺. This is in sharp contrast to the positive shifts of the corresponding waves of [Ru₃^II,III,III(渭₃-O)(渭-CH₃COO)₆(py)₂(CO)]. Density functional theory (DFT) calculations of [Ru₃^II,III,III(渭₃-O)(渭-CH₃COO)₆(py)₃], [Ru₃^II,III,III(渭₃-O)(渭-CH₃COO)₆(py)₂(CN)]^{鈭?/sup>, and [Ru₃II,III,III(渭₃-O)(渭-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 蟺 interactions of the two ligands with the triruthenium cores.}