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Updated: Dec 14, 2025
Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV
Published on: December 29, 2016
Chalcogen-Expanded Unsaturated Silicon Clusters: Thia-, Selena-, and Tellurasiliconoids
Nadine E Poitiers1, Volker Huch1, Michael Zimmer1
1Krupp-Chair of Inorganic and General Chemistry, Saarland University, Campus Saarbrücken C4.1, 66123, Saarbrücken, Germany.
Abstract:
Reactions of silylenes with heavier chalcogens (E) typically result in Si=E double bonds or their π-addition products. In contrast, the oxidation of a silylene-functionalized unsaturated silicon cluster (siliconoid) with Group 16 elements selectively yields cluster expanded siliconoids Si7 E (E=S, Se, Te) fully preserving the unsaturated nature of the cluster scaffold as evident from the NMR signatures of the products. Mechanistic considerations by DFT calculations suggest the intermediacy of a Si6 siliconoid with exohedral Si=E functionality. The reaction thus may serve as model system for the oxidation of surface-bonded silylenes at Si(100) by chalcogens and their diffusion into the silicon bulk.
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