Synthesis and Characterization of an Azido-Bridged Dinuclear Ruthenium(II) Polypyridylamine Complex Forming a Mixed-Valence State

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• 作者：Misaki Makino ; Tomoya Ishizuka ; Shingo Ohzu ; Jiang Hua ; Hiroaki Kotani ; Takahiko Kojima
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：May 6, 2013
• 年：2013
• 卷：52
• 期：9
• 页码：5507-5514
• 全文大小：394K
• 年卷期：v.52,no.9(May 6, 2013)
• ISSN：1520-510X

文摘

We have synthesized a mononuclear ruthenium(II) azido complex (1) and a dinuclear ruthenium(II) 渭-azido complex (2) having N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine (N4Py) as a pentadentate ancillary ligand. In the crystal structure of 2, intramolecular 蟺鈥撓€ stacking was found between the pyridine rings of the two different N4Py ligands, contributing to stabilize the dinuclear 渭-azido structure. 蟺 donation from the HOMO 蟺* orbital of the 渭-azido ligand to the Ru鈥揘(pyr) bond increases the bond order between the terminal and central N atoms in the 渭-azido ligand to strengthen the N鈥揘 bonds of the 渭-azido ligand. The 渭-azido complex 2 was revealed to exhibit a stepwise oxidation behavior in CH₃CN to afford a Ru^II鈥撐?azido鈥揜u^III mixed-valence (MV) state upon one-electron oxidation. The MV state of one-electron-oxidized 2 was categorized in the Robin鈥揇ay class II with the electronic coupling constant (H_ab) of 570 cm^鈥?.