Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan.
J Am Chem Soc. 2011 Aug 3;133(30):11504-7. doi: 10.1021/ja205361a. Epub 2011 Jul 7.
The stable sulfur-substituted tetrahedrane derivatives 2-4 were synthesized by the reaction of tris(trimethylsilyl)tetrahedranyllithium 1 with diphenyl disulfide, bis(4-nitrophenyl) disulfide, and bis(2,4-dinitrophenyl) disulfide, respectively, and characterized by both NMR spectroscopy and X-ray crystallography. Phenylsulfonyltetrahedrane 5 was prepared by the reaction of 2 and m-chloroperbenzoic acid. The UV-vis absorption spectra of 2-4 suggested an interaction of the σ orbital of the tetrahedrane core and the lone-pair electrons on the sulfur atom, whereas no interaction for 5 was found. Thermal reactions of 2 and 5 are also reported; 2 underwent fragmentation into two acetylene molecules, whereas 5 gave the corresponding cyclobutadiene.
稳定的硫取代四面体衍生物 2-4 是通过三(三甲基硅基)四面体锂 1 与二苯基二硫醚、双(4-硝基苯基)二硫醚和双(2,4-二硝基苯基)二硫醚分别反应合成的，并通过 NMR 光谱和 X 射线晶体学进行了表征。苯磺酰基四面体 5 是通过 2 和间氯过苯甲酸反应制备的。2-4 的紫外可见吸收光谱表明四面体核心的 σ 轨道与硫原子上的孤对电子相互作用，而 5 则没有发现相互作用。还报道了 2 和 5 的热反应；2 发生了碎裂成两个乙炔分子，而 5 则生成了相应的环丁二烯。
