Thermal Reaction of Octasilacubane with Sulfur, Selenium, and Tellurium: Formation of Novel Cage Systems

Abstract

The thermal reaction of an octathexyloctasilacubane, R 8 Si 8 (R = thexyl: 1,1,2-trimethypropyl), with sulfur in a sealed tube gave a sulfur-inserted novel compound, R 8 Si 8 S, together with an unexpected ring-opening compound. The reaction with selenium in a similar condition gave a ring-opening compound exclusively. With tellurium, the thermal reaction of the octasilacubane resulted in the formation of a tellurium-inserted compound (R 8 Si 8 Te), which was decomposed in solution to give the octasilacubane and tellurium.

Chalcogen‐Expanded Unsaturated Silicon Clusters: Thia‐, Selena‐, and Tellurasiliconoids

“…In view of the tremendous importance of chalcogen‐containing silicon materials, [19] including sub‐valent varieties such as the famous “silicon monoxide”, [20] we contemplated the possibility of the incorporation of Group 16 elements as heteroatoms into the cluster core without compromising the siliconoid characteristics. A large variety of molecular model systems for silicon subchalcogenides has been described in recent years, which are strictly electron‐precise without exception and thus do not reflect the widely accepted assumption of nanoscalar cluster domains in these composite materials [18a–c] . N‐heterocyclic silylenes, for instance, are well‐known to readily undergo oxidation to the corresponding silanones and heavier versions thereof [21–24]…”