The bicyclic silicon(I) ring compound Si {N(SiMe )Mes} (2) was used as starting material in reactions with chalcogens and chalcogen transfer agents at low temperatures. This resulted in the selective formation of new cage compounds. With Me NO, a silicon oxide with adamantane-type cage 3 was isolated that represents the first isolated T silsesquioxane. Reactions with propylenesulfide and red selenium gave direct access to defect heterocubane-type cages 4 and 5 with three Si-Si bonds wherein the silicon atoms adopt different low oxidation states of +I and +III. A reaction with elemental tellurium even occurs below room temperature to provide ditelluro-tetrasila-tricyclohexane 6.

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http://dx.doi.org/10.1002/chem.202302766DOI Listing

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