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Transition-Metal Complexes Featuring Dianionic Heavy Group 14 Element Aromatic Ligands
Accounts of Chemical Research ( IF 18.3 ) Pub Date : 2017-12-20 00:00:00 , DOI: 10.1021/acs.accounts.7b00367
Masaichi Saito 1
Affiliation  

The synthesis of dilithio-stannoles and -plumboles, dianionic aromatic compounds containing tin and lead atoms in their π-skeletons, opened a new field of transition-metal chemistry. Since the discovery of ferrocene (Cp2Fe), which is composed of anionic aromatic ligands (Cp: cyclopentadienyl) and Fe(II), ferrocene-type sandwich complexes have long played important roles in many fields of chemistry. During the last few decades, the electronic and structural properties of the Cp ligand have been modified by introducing electron-donating, electron-withdrawing, and sterically encumbered substituents on the skeletal carbon atoms to obtain desirable properties of the resulting sandwich complexes. In terms of modifying the Cp ligand, we focused our attention on introducing a heavy group 14 atom into the π-skeleton. This idea was originally inspired by a question of whether or not aromaticity was retained after the replacement of a skeletal carbon atom by a heavy group 14 atom. After we succeeded in the synthesis of aromatic dilithio-stannoles and -plumboles, revealing that the concept of conventional aromaticity was expanded to lead-containing π-systems, we undertook the present project on applying these dianionic aromatic heavy Cp analogues as ligands for transition-metal complexes. The combination of a stannole and Cp*Ru units accomplished the creation of a neutral triple-decker complex and an anionic ruthenocene, which was not be accessible using Cp and its related ligands that are composed of only carbon atoms. The anionic ruthenocene reacted with electrophiles to afford ruthenocene-type sandwich complexes, and the structures of the stannole skeletons were highly dependent on the substituents on the tin atoms, in sharp contrast to the planar Cp ligand. The dianionic plumbole ligand was also found to function as an η5-coordinating ligand in an anionic ruthenocene, which is noteworthy in terms of incorporating the heaviest group 14 atom into a π-ligand to produce a ferrocene-type sandwich complex. The anionic ruthenocene bearing the plumbole ligand reacted with electrophiles to afford ruthenocene-type plumbole complexes, which have oxidation potentials lower than those of the corresponding tin analogues, demonstrating the effect of introduction of a lead atom heavier than a tin atom. In the reactions of dilithiostannoles with group 4 metals, the resulting complexes were found to have exotic electronic structures that cannot be constructed by the Cp ligand. The transition-metal complexes derived from dilithio-stannoles and -plumbole therefore exhibit remarkable differences as well as similarities to the traditional Cp-based transition-metal complexes. These results spotlight the introduction of heavy group 14 atoms into carbon-based π-skeletons, which can perturb the electronic properties of conventional transition-metal complexes and open a new chemistry of transition-metal complexes.

中文翻译:

过渡金属配合物,具有重离子14族芳族配体

二硫代锡酮和-plumboles的合成是π骨架中含有锡和铅原子的二价芳族化合物,开辟了过渡金属化学的新领域。自发现二茂铁以来(Cp 2Fe)由阴离子芳族配体(Cp:环戊二烯基)和Fe(II)组成,二茂铁型夹心复合物在许多化学领域中长期发挥着重要作用。在过去的几十年中,通过在骨架碳原子上引入给电子,吸电子和空间受限的取代基来修饰Cp配体的电子和结构性质,以获得所需的所得夹心络合物的性质。在修饰Cp配体方面,我们将注意力集中在将重基14个原子引入π骨架上。这个想法最初是受到一个问题的启发,该问题是在骨架碳原子被14号重原子取代后是否保留芳香性。在我们成功合成了芳族二硫代锡醇和-plumboles之后,揭示了常规芳香性的概念已扩展到含铅的π系统,我们承担了将这些双阴离子芳香族重Cp类似物用作过渡金属配合物配体的本项目。锡环和Cp * Ru单元的组合完成了中性三层配合物和阴离子钌茂茂的合成,而Cp及其仅由碳原子组成的相关配体是无法获得的。阴离子钌茂金属与亲电试剂反应得到钌茂金属型夹心复合物,与平面Cp配体形成鲜明对比的是,锡环骨架的结构高度依赖于锡原子上的取代基。还发现二价铅铅配体起η的作用 我们承担了将这些双阴离子芳族重Cp类似物用作过渡金属配合物配体的项目。锡环和Cp * Ru单元的组合完成了中性三层配合物和阴离子钌茂茂的合成,而Cp及其仅由碳原子组成的相关配体是无法获得的。阴离子钌茂金属与亲电试剂反应得到钌茂金属型夹心复合物,与平面Cp配体形成鲜明对比的是,锡环骨架的结构高度依赖于锡原子上的取代基。还发现二价铅铅配体起η的作用 我们承担了将这些双阴离子芳族重Cp类似物用作过渡金属配合物配体的项目。锡环和Cp * Ru单元的组合完成了中性三层配合物和阴离子钌茂茂的合成,而Cp及其仅由碳原子组成的相关配体是无法获得的。阴离子钌茂金属与亲电试剂反应得到钌茂金属型夹心复合物,与平面Cp配体形成鲜明对比的是,锡环骨架的结构高度依赖于锡原子上的取代基。还发现二价铅铅配体起η的作用 锡环和Cp * Ru单元的组合完成了中性三层配合物和阴离子钌茂茂的合成,而Cp及其仅由碳原子组成的相关配体是无法获得的。阴离子钌茂金属与亲电试剂反应得到钌茂金属型夹心复合物,与平面Cp配体形成鲜明对比的是,锡环骨架的结构高度依赖于锡原子上的取代基。还发现二价铅铅配体起η的作用 锡环和Cp * Ru单元的组合完成了中性三层配合物和阴离子钌茂茂的合成,而Cp及其仅由碳原子组成的相关配体是无法获得的。阴离子钌茂金属与亲电试剂反应得到钌茂金属型夹心复合物,与平面Cp配体形成鲜明对比的是,锡环骨架的结构高度依赖于锡原子上的取代基。还发现二价铅铅配体起η的作用 与平面Cp配体形成鲜明对比的是,锡环骨架的结构高度依赖于锡原子上的取代基。还发现二价铅铅配体起η的作用 与平面Cp配体形成鲜明对比的是,锡环骨架的结构高度依赖于锡原子上的取代基。还发现二价铅铅配体起η的作用5阴离子钌茂金属中的α-配位配体,就将最重的14族原子掺入π-配体产生二茂铁型夹心复合物而言,这是值得注意的。带有铅原子配体的阴离子钌茂金属与亲电试剂反应,得到钌茂金属型铅茂复合物,其氧化电位低于相应的锡类似物的氧化电位,这表明引入了比锡原子重的铅原子的作用。在二硫代锡锡诺与第4组金属的反应中,发现所得配合物具有奇异的电子结构,无法由Cp配体构造。因此,衍生自二硫代锡酚和-铅的过渡金属配合物与传统的基于Cp的过渡金属配合物表现出显着的差异和相似性。
更新日期:2017-12-20
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