(η4-Butadiene)Sn(0) Complexes: A New Approach for Zero-Valent p-Block Elements Utilizing a Butadiene as a 4π-Electron Donor
(η4-Butadiene)Sn(0) Complexes: A New Approach for Zero-Valent p-Block Elements Utilizing a Butadiene as a 4π-Electron Donor
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DOI：
10.1021/jacs.6b07304
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发表时间：
2016-09-07
影响因子：
15
通讯作者：
Saito, Masaichi
中科院分区：
文献类型：
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作者：
Kuwabara, Takuya;Nakada, Marisa;Saito, Masaichi
零价p-块元素的研究是合成化学和理论化学领域的一个新的热点，因为它们的新颖电子态在S轨道和p-轨道上都有两个孤子对。人们认为，具有大取代基的sigma供体配体对于稳定这些物种是必不可少的。在这里，我们提出了一种新的方法，使用丁二烯作为4π电子供体来稳定零价族14元素。在我们探索锡环戊二烯配体配位化学的研究中，得到了意想不到的产物，其中锡原子与丁二烯以ETA(4)-方式配位。由于丁二烯是中性的4pi电子给体，产物中锡原子的形式氧化数应该为零，这一点得到了X射线衍射分析和理论计算的支持。并对产物的形成机理进行了描述。
Research on zero-valent p-block elements is a recent hot topic in synthetic and theoretical chemistry because of their novel electronic states having two lone pairs in both the s- and p-orbitals. It is considered that sigma-donating ligands bearing large substituents are essential to stabilize these species. Herein, we propose a new approach using butadiene as a 4 pi-electron donor to stabilize zero-valent group 14 elements. During our study to explore the coordination chemistry of stannacyclopentadienyl ligands, unexpected products, in which the tin atom is coordinated by a butadiene in a eta(4)-fashion, were obtained. Because butadiene is a neutral 4 pi-electron donating ligand, the formal oxidation number of the tin atoms of the products should be zero, which is supported by X-ray diffraction analysis and theoretical calculations. A mechanism for the formation of the products is also described.