Synthesis, characterization, and detailed electrochemistry of binuclear ruthenium(III) complexes bridged by bisacetylacetonate.: Crystal and molecular structures of [{Ru(acac)2}2(tae)] (acac=2,4-pentanedionate ion, tae=1,1,2,2-tetraacetylethanate dianion)
Synthesis, characterization, and detailed electrochemistry of binuclear ruthenium(III) complexes bridged by bisacetylacetonate.: Crystal and molecular structures of [{Ru(acac)2}2(tae)] (acac=2,4-pentanedionate ion, tae=1,1,2,2-tetraacetylethanate dianion)
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DOI：
10.1021/ic030216c
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发表时间：
2004-10-04
影响因子：
4.6
通讯作者：
Shimizu, K
中科院分区：
文献类型：
--
作者：
Koiwa, T;Masuda, Y;Shimizu, K
合成了双核β -二酮托钌（III）配合物[{Ru(acac)(2)}(2)(tae)]、[{Ru(phpa)(2)}(2)(tae)]和[(acac)(2))Ru(tae)Ru(phpa)(2)]以及双核和单核联吡啶配合物[{Ru(bpy)(2)}(2)(tae)](PF6)(2)和[Ru(bpy)(2)（Htae)]PF6 （acac = 2,4-戊二酸盐离子，phpa = 2,2,6,6-四甲基-3,5-庚二酸盐离子，tae = 1,1,2,2-四乙酰乙二酸盐，bpy = 2,2'-联吡啶））。新的配合物已通过核磁共振、质谱和电子能谱数据进行了表征。[{Ru(acac)(2)}(2)(tae)]的晶体和分子结构已通过单晶x射线衍射研究得到了解析。[{Ru(acac)(2)}(2)(tae)]中位异构体的晶体数据已被二面角结果证实，桥接tae配体的两个乙酰丙酮单元几乎彼此垂直。对双核配合物的电化学进行了详细的研究。将双核配合物的电化学行为细节与从相应的双核配合物的半结构得到的单核配合物的电化学行为细节进行了比较。溶剂对Ru-II-Ru-III和Ru-III-Ru-IV络合物混合价态的影响已经通过各种伏安和电谱技术进行了研究。得到了配比常数K-c与溶剂给体数之间的关系。双核配合物的K-c值较低，因为桥接tae配体的两个乙酰丙酮单元不在同一平面上，如[{Ru(acaC)(2)}(2)(tae)]的晶体结构所示。
Binuclear beta-diketonatoruthenium(III) complexes [{Ru(acac)(2)}(2)(tae)], [{Ru(phpa)(2)}(2)(tae)], and [(acac)(2)Ru(tae)Ru(phpa)(2)] and binuclear and mononuclear bipyridine complexes [{Ru(bpy)(2)}(2)(tae)](PF6)(2) and [Ru(bpy)(2)(Htae)]PF6 (acac = 2,4-pentanedionate ion, phpa = 2,2,6,6-tetramethyl-3,5-heptanedionate ion, tae = 1,1,2,2-tetraacetylethanate dianion, and bpy = 2,2'-bipyridine) were synthesized. The new complexes have been characterized by H-1 NMR, MS, and electronic spectral data. Crystal and molecular structures of [{Ru(acac)(2)}(2)(tae)] have been solved by single-crystal X-ray diffraction studies. Crystal data for the meso isomer of [{Ru(acac)(2)}(2)(tae)] have been confirmed by the dihedral angle result that two acetylacetone units of the bridging tae ligand are almost perpendicular to one another. A detailed investigation on the electrochemistry of the binuclear complexes has been carried out. The electrochemical behavior details of the binuclear complexes have been compared with those of the mononuclear complexes obtained from the half-structures of the corresponding binuclear complexes. Studies on the effects of solvents on the mixed-valence states of Ru-II-Ru-III and Ru-III-Ru-IV complexes have been carried out by various voltammetric and electrospectroscopic techniques. A correlation between the comproportionation constant (K-c) and the donor number of the solvent has been obtained. The K-c values for the binuclear complexes have been found to be low because of the fact that two acetylacetone units of the bridging tae ligand are not in the same plane, as revealed by the crystal structure of [{Ru(acaC)(2)}(2)(tae)].