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New Polydentate Trimethylsilyl Chalcogenide Reagents for the Assembly of Polyferrocenyl Architectures

机译:用于聚二茂铁基结构组装的新型多齿三甲基硅烷基硫属元素化物试剂

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A series of polychalcogenotrimethylsilane complexes Ar(CH_2ESiMe_3)_n, (Ar=aryl; E=S, Se; n=2, 3, and 4) can be prepared from the corresponding polyorganobromide and M[ESiMe_3] (M=Na, Li). These represent the first examples of the incorporation of such a large number of reactive -ESiMe_3 moieties onto an organic molecular framework. They are shown to be convenient reagents for the preparation of the polyferrocenylseleno- and thioesters from ferrocenoyl chloride. The synthesis, structures, and spectroscopic properties of the new silyl chalcogen complexes 1,4- (Me_3SiECH_2)_2(C_6Me_4) (E=S, 1; E=Se, 2), 1,3,5-(Me_3SiECH_2)_3- (C_6Me_3) (E=S, 3; E=Se, 4) and 1,2,4,5-(Me_3SiECH_2)_4(C_6H_2) (E=S, 5; E=Se, 6) and the polyferrocenyl chalcogenoesters [1,4-{FcC(O)ECH_2}_2(C_6Me_4)] (E=S, 7; E=Se, 8), [1,3,5- {FcC(O)ECH_2}_3(C_6Me_3)] (E=S, 9; E=Se, 10) and [1,2,4,5- {FcC(O)ECH_2}_4(C_6H_2)] (E=S, 11 illustrated; E=Se, 12) are reported. The new polysilylated reagents and polyferrocenyl chalcogenoesters have been characterized by multinuclear NMR spectroscopy (~1H, ~(13)C, ~(77)Se), electrospray ionization mass spectrometry and, for complexes 1, 2, 3, 4, 7, 8, and 11, single-crystal X-ray diffraction. The cyclic voltammograms of complexes 7–11 are presented.
机译:可以从相应的聚有机溴化物和M [ESiMe_3](M = Na,Li)制备一系列聚硫代三甲基硅烷配合物Ar(CH_2ESiMe_3)_n,(Ar =芳基; E = S,Se; n = 2、3和4) 。这些代表了将如此大量的反应性-ESiMe_3部分结合到有机分子框架上的第一个例子。已显示它们是从二茂铁酰氯制备聚二茂铁烯基硒酸酯和硫代酸酯的方便试剂。新型甲硅烷基硫族元素配合物1,4-(Me_3SiECH_2)_2(C_6Me_4)(E = S,1; E = Se,2),1,3,5-(Me_3SiECH_2)_3-的合成,结构和光谱性质(C_6Me_3)(E = S,3; E = Se,4)和1,2,4,5-(Me_3SiECH_2)_4(C_6H_2)(E = S,5; E = Se,6)和聚二茂铁硫属元素酯[ 1,4- {FcC(O)ECH_2} _2(C_6Me_4)](E = S,7; E = Se,8),[1,3,5- {FcC(O)ECH_2} _3(C_6Me_3)]( E = S,9; E = Se,10)和[1,2,4,5- {FcC(O)ECH_2} _4(C_6H_2)](E = S,插图11; E = Se,12) 。通过多核NMR光谱(〜1H,〜(13)C,〜(77)Se),电喷雾电离质谱对复合物1,2、3、4、7、8进行了表征和11,单晶X射线衍射。给出了配合物7-11的循环伏安图。

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