Iijima Keisuke, Sugamata Koh, Sasamori Takahiro
Graduate School of Science and Technology, University of Tsukuba, 1-1-1 Tennoudai, Tsukuba 305-8571, Ibaraki, Japan.
Department of Chemistry, Institute of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennoudai, Tsukuba 305-8571, Ibaraki, Japan.
Molecules. 2025 Jun 30;30(13):2826. doi: 10.3390/molecules30132826.
Heavier element analogues of a ketone, a C=O double-bond compound, have been fascinating compounds from the viewpoint of main-group element chemistry because of their unique structural features and reactivity as compared with those of a ketone, which plays an important role in organic chemistry. We will report here the synthesis of diorgano-stannanethione and stannaneselone featuring tin-chalcogen double bonds, which are the heavy-element analogues of a ketone. The newly obtained stannaneselone has been structurally characterized by spectroscopic analyses and single-crystal X-ray diffraction (SC-XRD) analysis, showing the short Sn-Se bond length featuring π-bond character. The obtained bis(ferrocenyl)stannanechalcogenones were found to undergo [2+4]cycloaddition reactions with 2,3-dimethyl-1,3-butadiene, affording the corresponding six-membered ring compound. Notably, thermolysis of the [2+4]cycloadduct of the stannaneselone regenerated the stannaneselone via the retro[2+4]cycloaddition, whereas the sulfur analogue was thermally very stable.
与酮（在有机化学中起重要作用的C=O双键化合物）相比，酮的重元素类似物由于其独特的结构特征和反应性，从主族元素化学的角度来看一直是引人入胜的化合物。我们在此将报道二有机锡硫酮和具有锡-硫族元素双键的锡硒酮的合成，它们是酮的重元素类似物。新得到的锡硒酮已通过光谱分析和单晶X射线衍射（SC-XRD）分析进行了结构表征，显示出具有π键特征的短Sn-Se键长。发现所得到的双（二茂铁基）锡硫族酮与2,3-二甲基-1,3-丁二烯发生[2+4]环加成反应，生成相应的六元环化合物。值得注意的是，锡硒酮的[2+4]环加成产物热解通过逆[2+4]环加成再生出锡硒酮，而硫类似物在热方面非常稳定。
