Synthesis and Characterization of an Azido-Bridged Dinuclear Ruthenium(II) Polypyridylamine Complex Forming a Mixed-Valence State
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Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, Japan
*E-mail: [email protected]
Abstract
We have synthesized a mononuclear ruthenium(II) azido complex (1) and a dinuclear ruthenium(II) μ-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 π–π stacking was found between the pyridine rings of the two different N4Py ligands, contributing to stabilize the dinuclear μ-azido structure. π donation from the HOMO π* orbital of the μ-azido ligand to the Ru–N(pyr) bond increases the bond order between the terminal and central N atoms in the μ-azido ligand to strengthen the N–N bonds of the μ-azido ligand. The μ-azido complex 2 was revealed to exhibit a stepwise oxidation behavior in CH3CN to afford a RuII–μ-azido–RuIII mixed-valence (MV) state upon one-electron oxidation. The MV state of one-electron-oxidized 2 was categorized in the Robin–Day class II with the electronic coupling constant (Hab) of 570 cm–1.
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