Heterometallic Complexes with Re−Bi Metal Bonds
Heterometallic Complexes with Re−Bi Metal Bonds
复制标题
具有 Re−Bi 金属键的异金属配合物
DOI：
10.1021/om100011r
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发表时间：
2010
期刊：
影响因子：
2.8
通讯作者：
C. Limberg
中科院分区：
文献类型：
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作者：
Rafael Schiwon;Christina Knispel;C. Limberg
茂金属氢化物与铋的反应生成了Re-−-Bi金属键的络合物，并伴随着相应醇的生成。因此，可以从一元醇盐[(MeO)Bi(o-−)2]n和三醇盐[BiOCH(CF3)2}3(THF)]2获得[Cp2Re CF3 BiR2]类型的化合物，对于这些化合物，原则上也可以进行多个取代反应，但由于六氟异丙基的吸电子特性而被禁止。相应地，含有富电子叔丁基团的三元醇盐[Bi(OtBu)3]确实会导致多个取代事件：首先，它与两个等价物[Cp2ReH]反应，得到中间体[(Cp2Re)2Bi(OtBu)]，由于它通过CcP−H键的裂解进行了分子内的醇消除，因此无法分离。这导致了配合物[Cpre(μ-η5，η1-C5H4)Bi−ReCp2]，具有弯曲的Bi−C键，使得一个去质子化的Cp配体桥接了Bi−Re金属键。所有的化合物都经过了完全的查拉...
The reaction of rhenocene hydride with bismuth alkoxides leads to complexes containing Re−Bi metal bonds with concomitant formation of the corresponding alcohols. Hence, compounds of the type [Cp2Re−BiR2] can be obtained from the monoalkoxide [(MeO)Bi(o-tol)2]n and also from the trialkoxide [Bi{OCH(CF3)2}3(thf)]2, for which in principle also multiple substitution reactions would have been possible, but are prohibited by the electron-withdrawing character of the hexafluoroisopropyl groups. Correspondingly, the trialkoxide [Bi(OtBu)3] containing electron-rich tert-butyl groups does lead to multiple substitution events: First of all it reacts with two equivalents of [Cp2ReH] to give the intermediate [(Cp2Re)2Bi(OtBu)], which could not be isolated, since it undergoes an intramolecular alcohol elimination via CpC−H bond cleavage. This results in the complex [CpRe(μ-η5,η1-C5H4)Bi−ReCp2], featuring a bent Bi−C bond so that one deprotonated Cp ligand bridges a Bi−Re metal bond. All compounds have been fully chara...