Sulfur-Substituted Tetrahedranes

详细信息    查看全文

• 作者：Tatsumi Ochiai ; Masaaki Nakamoto ; Yusuke Inagaki ; Akira Sekiguchi
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：August 3, 2011
• 年：2011
• 卷：133
• 期：30
• 页码：11504-11507
• 全文大小：744K
• 年卷期：v.133,no.30(August 3, 2011)
• ISSN：1520-5126

文摘

The stable sulfur-substituted tetrahedrane derivatives 2鈥?b>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鈥搗is absorption spectra of 2鈥?b>4 suggested an interaction of the 蟽 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.