Department of Chemistry, College of Science, Rikkyo University, 3-34-1 Nishi-Ikebukuro, Toshima-ku, Tokyo, 171-8501, Japan.
Materials Characterization Support Unit, RIKEN Center for Emergent Matter Science (CEMS), 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan.
Chemistry. 2018 May 11;24(27):6922-6926. doi: 10.1002/chem.201800828. Epub 2018 Apr 26.
Bis(methylene)-λ -sulfane 1, a >C=S=C< heterocumulene, was obtained as a red crystalline solid from the reaction between elemental sulfur and a carbenoid that contains sterically demanding silylalkyl groups. Under atmospheric conditions, and even at elevated temperatures, 1 exhibits extraordinary stability. The molecular structure and electron-density distribution of 1 were analyzed by single-crystal X-ray diffraction analysis, which revealed a bent C=S=C geometry with C=S=C π-bonds. These results, combined with those of variable-temperature NMR measurements and theoretical calculations suggest a slow rotation of the S=C moieties in 1, the stability and structure of which were further examined by theoretical calculations.
双（亚甲基）-λ - 硫杂环丙烯 1 是一种 >C=S=C<杂cumulene，它是通过元素硫与含有空间位阻硅烷基的碳烯反应得到的红色晶体固体。在大气条件下，甚至在高温下，1 表现出非凡的稳定性。通过单晶 X 射线衍射分析对 1 的分子结构和电子密度分布进行了分析，结果表明其具有弯曲的 C=S=C 几何形状和 C=S=C π 键。这些结果与变温 NMR 测量和理论计算的结果相结合，表明 1 中 S=C 部分的缓慢旋转，其稳定性和结构进一步通过理论计算进行了检验。
