The formal combination of three singlet biradicaloid entities to a singlet hexaradicaloid metalloid Ge14[Si(SiMe3)3]5[Li(THF)2]3 cluster.
The formal combination of three singlet biradicaloid entities to a singlet hexaradicaloid metalloid Ge14[Si(SiMe3)3]5[Li(THF)2]3 cluster.
复制标题
三个单线态双自由基实体与单线态六自由基准金属 Ge14[Si(SiMe3)3]5[Li(THF)2]3 簇的正式组合
DOI：
10.1021/ja107446z
复制
发表时间：
2011
影响因子：
15
通讯作者：
A. Schnepf
中科院分区：
文献类型：
--
作者：
C. Schenk;A. Kracke;K. Fink;A. Kubas;W. Klopper;M. Neumaier;H. Schnöckel;A. Schnepf
GeBr与LiSi（SiMe 3）3反应生成类金属簇合物[（THF）2Li] 3Ge 14 [Si（SiMe 3）3]5（1）。在介绍了第一个由14个锗原子组成的空多面体[（THF）2Li] 3Ge 14 [Ge（SiMe 3）3]5（2）之后，我们对1进行了进一步的研究，以获得对其化学和成键性质的初步认识。用同步辐射X射线晶体结构测定了1的分子结构。通过量子化学计算进一步研究了Ge 14多面体的电子结构，结果表明，Ge 14多面体的三个单重双自由基实体形式上联合收割机结合产生了Ge 14多面体的单重六自由基特征。此外，在通过螯合配体消除[Li（THF）2]+基团之后的1的初始反应（例如，TMEDA或12-冠-4）。在气相中的碰撞诱导解离实验，采用FT-ICR质谱，导致消除的单重biradicaloid Ge 5 H2 [Si（SiMe 3）3] 2集群。类金属团簇1独特的多自由基键合特性可能被用作表面科学和纳米技术领域的反应和性质的模型。
The reaction of GeBr with LiSi(SiMe3)3leads to the metalloid cluster compound [(THF)2Li]3Ge14[Si(SiMe3)3]5(1). After the introduction of a first cluster of this type, in which 14 germanium atoms form an empty polyhedron, [(THF)2Li]3Ge14[Ge(SiMe3)3]5(2), we present here further investigations on1to obtain preliminary insight into its chemical and bonding properties. The molecular structure of1is determined via X-ray crystal structure solution using synchrotron radiation. The electronic structure of the Ge14polyhedron is further examined by quantum chemical calculations, which indicate that three singlet biradicaloid entities formally combine to yield the singlet hexaradicaloid character of1. Moreover, the initial reactions of1after elimination of the [Li(THF)2]+groups by chelating ligands (e.g., TMEDA or 12-crown-4) are presented. Collision induced dissociation experiments in the gas phase, employing FT-ICR mass spectrometry, lead to the elimination of the singlet biradicaloid Ge5H2[Si(SiMe3)3]2cluster. The unique multiradicaloid bonding character of the metalloid cluster1might be used as a model for reactions and properties in the field of surface science and nanotechnology.