A Stable Dimer of SiS2 Arranged between Two Carbene Molecules

The Me-cAAC:-stabilized dimer of silicon disulfide (SiS2) has been isolated in the molecular form as (Me-cAAC:)(2)Si2S4 (2) at room temperature [Me-cAAC:=cyclic alkyl(amino) carbene]. Compound 2 has been synthesized from the reaction of (Me-cAAC:)(2)Si-2 with elemental sulfur in a 1:4 molar ratio under oxidative addition. This is the smallest molecular unit of silicon disulfide characterized by X-ray crystallography, electron ionization mass spectrometry, and NMR spectroscopy. Structures with three sulfur atoms arranged around a silicon atom are known; however, 2 is the first structurally characterized silicon-sulfur compound containing one terminal and two bridging sulfur atoms at each silicon atom. Compound 2 shows no decomposition after storing for three months in an inert atmosphere at ambient temperature. The bonding of 2 has been further studied by theoretical calculations.