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Bismuthanides and Bismuthanediides − Synthesis and Structural Characterization of [R2Bi] and [(RBi)12Na21]3 Salts with Bulky Silyl Substituents
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2002
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Materials ScienceInorganic ChemistryStructural CharacterizationInorganic CompoundEngineeringBulky Silyl SubstituentsCoordination ComplexAlkali Metal BismuthanidesMain Group ChemistryChemistryBismuthanediides − SynthesisTwo-coordinate Bismuth AtomCrystallographyInorganic SynthesisBismuth Trihalides
The reaction of bismuth trihalides with the bulky alkali metal silanides [(THF)3LiSi(SiMe3)3] and [(THF)2NaSi(CMe3)3] affords the cyclotetrabismuthanes (RBi)4 1 and 3, the alkali metal bismuthanides [Li(THF)4][Bi{Si(SiMe3)3}2] (2) and Na(THF)3[Bi{Si(CMe3)3}]2 (4) and the bismuthanediide Na3(THF)14[Na21{BiSi(CMe3)3}12] (5). Compound 2 features a two-coordinate bismuth atom. The core of 5 is a Bi12 icosahedron which is face-capped by 20 sodium atoms. The cluster is filled with a sodium atom. All structures were confirmed by single crystal X-ray crystallography. In addition, the bismuthanides and bismuthanediides were investigated by quantum chemical calculations. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)