Jaroentomeechai Thapakorn, Yingsukkamol Pa-Kwan, Phurat Chuttree, Somsook Ekasith, Osotchan Tanakorn, Ervithayasuporn Vuthichai
Department of Chemistry and Center of Excellence for Innovation in Chemistry (PERCH-CIC), ‡Department of Physics, and §Capability Building Unit for Nanoscience and Nanotechnology, Faculty of Science, Mahidol University , Rama VI road, Ratchathewi, Bangkok 10400, Thailand.
Inorg Chem. 2012 Nov 19;51(22):12266-72. doi: 10.1021/ic3015145. Epub 2012 Nov 7.
Novel phthalimide and o-sulfobenzimide-functionalized silsesquioxanes were successfully synthesized via nucleophilic substitution reactions from octakis(3-chloropropyl)octasilsesquioxane. Surprisingly, the formation of deca- and dodecasilsesquioxanes cages was discovered during substitution with phthalimide, but only octasilsesquioxane maintained a cage in the o-sulfobenzimide substitution reaction. Moreover, we report the electronic effect of nitrogen nucleophiles to promote cage-rearrangement of inorganic silsesquioxane core for the first time. Structures of products were confirmed by (1)H, (13)C, and (29)Si NMR spectroscopy, ESI-MS analysis, and single-crystal X-ray diffraction.
通过八（3-氯丙基）倍半硅氧烷的亲核取代反应成功合成了新型邻苯二甲酰亚胺和邻磺酰苯甲酰亚胺官能化的倍半硅氧烷。令人惊讶的是，在用邻苯二甲酰亚胺取代过程中发现了十聚和十二聚倍半硅氧烷笼的形成，但在邻磺酰苯甲酰亚胺取代反应中只有八聚倍半硅氧烷保持笼状结构。此外，我们首次报道了氮亲核试剂促进无机倍半硅氧烷核心笼重排的电子效应。通过（1）H、（13）C和（29）Si核磁共振光谱、电喷雾电离质谱分析和单晶X射线衍射对产物结构进行了确认。
