A Striking Mode of Activation of Carbon Disulfide with a Cooperative Bis(silylene)

Abstract

The reactivity of the 1,4-substituted bis(silylenyl)terphenylene 1, 1,4-[ortho-(LSi)C₆ H₄ ]₂ C₆ H₄ , (L=RC(NtBu)₂ , R=Ph, Mes) towards CS₂ is reported. It results in a dearomatization of the phenylene ring, affording the 1,3-substituted cyclohexadiene derivative 2. According to DFT calculations, a transient silene containing a Si=C bond capable of π(C=C) addition at the aromatic phenylene ring is a key intermediate. In contrast, addition of CS₂ to the biphenyl-substituted mono-silylene ortho-(LSi)C₆ H₄ -C₆ H₅ 3 leaves the aromatic π-system intact and forms, in a [1+2] cycloaddition reaction, the corresponding thiasilirane 4 with a three-membered SiSC ring. Further experimental studies led to the isolation of the novel mesoionic five-membered Si₂ S₂ C heterocycle 6, which reacts with CS₂ under C-C bond formation. All isolated new compounds were fully characterized and their molecular structures determined by single-crystal X-ray diffraction analyses.