Synthesis and Structure of a Stable Bis(methylene)-λ4-sulfane
Synthesis and Structure of a Stable Bis(methylene)-λ4-sulfane
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稳定双(亚甲基)-λ4-硫烷的合成与结构
DOI：
10.1002/chem.201800828
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发表时间：
2018
期刊：
影响因子：
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通讯作者：
Ishii Shigeru
中科院分区：
文献类型：
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作者：
Sugamata Koh;Hashizume Daisuke;Suzuki Yuko;Sasamori Takahiro;Ishii Shigeru
双（亚甲基）-λ4-硫烷1，a >C=S=C<杂累积苯，作为红色结晶固体由元素硫和含有空间要求高的甲硅烷基烷基的类卡宾之间的反应获得。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射线衍射分析了1的分子结构和电子密度分布，发现其具有弯曲的C=S=C几何构型和C=S=C π-键。结合变温NMR测量和理论计算的结果，这些结果表明1中的S=C部分的缓慢旋转，其稳定性和结构通过理论计算进一步检查。
Bis(methylene)‐λ4‐sulfane1, 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,1exhibits extraordinary stability. The molecular structure and electron‐density distribution of1were 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 in1, the stability and structure of which were further examined by theoretical calculations.