Heterotrimetallic M−M′−M′′ Transition Metal Complexes Based on 1,3,5-Triethynylbenzene: Synthesis, Solid State Structure, and Electrochemical and UV−Vis Characterization. EPR Analysis of the in Situ Generated Associated Radical Cations
Heterotrimetallic M−M′−M′′ Transition Metal Complexes Based on 1,3,5-Triethynylbenzene: Synthesis, Solid State Structure, and Electrochemical and UV−Vis Characterization. EPR Analysis of the in Situ Generated Associated Radical Cations
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基于 1,3,5-三乙炔基苯的异三金属 M−M′−M′′ 过渡金属配合物：合成、固态结构以及原位生成的相关自由基阳离子的电化学和紫外-可见光表征。
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发表时间：
2008
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通讯作者：
H. Lang
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作者：
Rico Packheiser;P. Ecorchard;T. Rüffer;M. Lohan;B. Bräuer;F. Justaud;C. Lapinte;H. Lang
讨论了一系列具有不同有机金属结构单元的配合物的合成，这些结构单元不对称地排列在 1,3,5-三乙炔基苯核心的外围。它们可以通过不同的连续反应序列获得，从而允许引入过渡金属单元，例如 Fc、[(tBu2bpy)(CO)3Re]、[(η5-C5H5)(Ph3P)2Ru]、[(η5-C5H5)(Ph3P)2Os] 和反式-[(Ph3P)2(Cl)Pt] (Fc = (η5-C5H5)(η5-C5H4)Fe； tBu2bpy = 4,4'-二叔丁基-2,2'-联吡啶）。已确定了五种配合物的固态结构。对新合成的单金属、异双金属和异三金属组件的电化学行为进行了研究，结果表明各个金属原子之间不存在显着的电子相互作用。紫外可见光谱测量表明适当的金属原子之间存在弱相互作用。相关的自由基阳离子是通过逐步化学氧化原位产生的，并通过连续波电子顺磁共振（EPR）进行表征...
The synthesis of a series of complexes with different organometallic building blocks unsymmetrically arranged around the periphery of a 1,3,5-triethynylbenzene core is discussed. They are accessible by diverse consecutive reaction sequences, which allow the introduction of transition metal units such as Fc, [(tBu2bpy)(CO)3Re], [(η5-C5H5)(Ph3P)2Ru], [(η5-C5H5)(Ph3P)2Os], and trans-[(Ph3P)2(Cl)Pt] (Fc = (η5-C5H5)(η5-C5H4)Fe; tBu2bpy = 4,4′-di-tert-butyl-2,2′-bipyridyl). The solid state structures of five complexes have been determined. The electrochemical behavior of the newly synthesized mono-, heterobi-, and heterotrimetallic assemblies have been studied, showing that there is no significant electronic interaction between the respective metal atoms. UV−vis spectroscopic measurements suggest a weak interaction between the appropriate metal atoms. The associated radical cations were in situ generated by stepwise chemical oxidation and characterized by continuous wave electron paramagnetic resonance (EPR) in...