Application of Bulky NHC–Rhodium Complexes in Efficient S–Si and S–S Bond Forming Reactions

[Image: see text] The efficient and straightforward syntheses of silylthioethers and disulfides are presented. The synthetic methodologies are based on new rhodium complexes containing bulky N-heterocyclic carbene (NHC) ligands that turned out to be efficient catalysts in thiol and thiol–silane coupling reactions. These green protocols, which use easily accessible reagents, allow obtaining compounds containing S–Si and S–S bonds in solvent-free conditions. Additionally, preliminary tests on coupling of mono- and octahydro-substituted spherosilicates with selected thiols have proved to be very promising and showed that these catalytic systems can be used for the synthesis of a novel class of functionalized silsesquioxane derivatives.