Bismuthanides and Bismuthanediides-Synthesis and Structural Characterization of [R_2Bi]~- and [RBi)_(12)Na_(21)]~(3-) Salts with Bulky Silyl Substituents

摘要

The reaction of bismuth trihalides with the bulky alkali metal silanides [(THF)_3LiSi(SiMe_3)_3] and [(THF)_2NaSi(CMe_3)_3] affords the cyclotetrabismuthanes (RBi)_4 1 and 3, the alkali metal bismuthanides [Li(THF)_4][Bi{Si(SiMe_3)_3}_2 (2) and Na(THF)_3[Bi{Si(CMe_3)_3}]_2 (4) and the bismuthanediide Na_3(THF)_(14)[Na_(21){BiSi(CMe_3)_3_(12)] (5). Compound 2 features a two-coordinate bismuth atom. The core of 5 is a Bi_(12) icosahedron which is face-capped by 20 sodium atoms. The cluster is filled with sodium atom. All structures were confirmed by single crystal X-ray crystallography. In addition, the bismuthanides and bismuthanediides were investigated by quantum chemical calculations.