A Striking Mode of Activation of Carbon Disulfide with a Cooperative Bis(silylene)
Marcel‐Philip Luecke, Luisa Giarrana, Arseni Kostenko, Tobias Gensch, Shenglai Yao, Matthias Drieß
Abstract
Abstract The reactivity of the 1,4‐substituted bis(silylenyl)terphenylene 1 , 1,4‐[ ortho ‐(LSi)C 6 H 4 ] 2 C 6 H 4 , (L=RC(NtBu) 2 , R=Ph, Mes) towards CS 2 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 CS 2 to the biphenyl‐substituted mono‐silylene ortho ‐(LSi)C 6 H 4 ‐C 6 H 5 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 Si 2 S 2 C heterocycle 6 , which reacts with CS 2 under C−C bond formation. All isolated new compounds were fully characterized and their molecular structures determined by single‐crystal X‐ray diffraction analyses.