Synthesis and reactivity of nitrogen nucleophiles-induced cage-rearrangement silsesquioxanes
Thapakorn Jaroentomeechai1, Pa-Kwan Yingsukkamol, Chuttree Phurat
1Department 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.
Abstract:
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.
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