The Formal Combination of Three Singlet Biradicaloid Entities to a Singlet Hexaradicaloid Metalloid Ge-14[Si(SiMe3)(3)](5)[Li(THF)(2)](3) Cluster

作者：Schenk Christian; Kracke Andreas; Fink Karin; Kubas Adam; Klopper Wim; Neumaier Marco; Schnoeckel Hansgeorg; Schnepf Andreas^*

来源：Journal of the American Chemical Society, 2011, 133(8): 2518-2524.

DOI：10.1021/ja107446z

The reaction of GeBr with LiSi(SiMe3)(3) leads to the metalloid cluster compound [(THF)(2)Li](3)Ge-14[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)(2)Li](3)-Ge-14[Ge(SiMe3)(3)](5) (2), we present here further investigations on 1 to obtain preliminary insight into its chemical and bonding properties. The molecular structure of 1 is determined via X-ray crystal structure solution using synchrotron radiation. The electronic structure of the Ge-14 polyhedron is further examined by quantum chemical calculations, which indicate that three sing et biradicaloid entities formally combine to yield the singlet hexaradicaloid character of 1. Moreover, the initial reactions of 1 after 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)](2) cluster. The unique multiradicaloid bonding character of the metalloid cluster 1 might be used as a model for reactions and properties in the field of surface science and nanotechnology.

• 出版日期2011-3-2