Amido Silicon Chalcogenide Compounds with Unprecedented Cluster Cores and Low Oxidation State Silicon Atoms

Reactions of the bicyclic silicon(I) ring compound [Si 4 {N(SiMe 3 )Dipp} 4 ] 1 with the chalcogens O 2 , Se, Te and the group 16 element compounds TeP( n Bu) 3 and Me 3 NO afforded unprecedented amido‐substituted cage compounds such as [Si 4 Se 3 {N(SiMe 3 )Dipp} 4 ] 3–5 with two different tricyclo‐heptane‐type cages and one with a defect‐hetero‐cubane‐type Si 4 Se 3 core, and [Si 4 Te 6 {N(SiMe 3 )Dipp} 4 ] 6 with an adamantane‐type cage. These compounds were examined by single‐crystal X‐ray diffraction, multinuclear NMR spectroscopy in solution, ESI mass spectrometry, UV/Vis spectroscopy, and DFT calculations.