Non-aqueous selective synthesis of orthosilicic acid and its oligomers

五十嵐 正安*; 松本 朋浩*; 八木橋 不二夫*; 山下 浩*; 大原 高志; 花島 隆泰*; 中尾 朗子*; 茂吉 武人*; 佐藤 一彦*; 島田 茂*

Nature Communications (Internet), 8, p.140_1 - 140_8, 2017/07

https://doi.org/10.1038/s41467-017-00168-5

Orthosilicic acid (Si(OH)) and its small condensation compounds are among the most important silicon compounds but have never been isolated, despite the long history of intense research due to their instability. These compounds would be highly useful building blocks for advanced materials if they become available at high purity. We developed a simple procedure to selectively synthesize orthosilicic acid, its dimer, cyclic trimer, and tetramer, as well as appropriate conditions to stabilize these species, in organic solvents. Isolation of orthosilicic acid, the dimer and the cyclic tetramer as hydrogen-bonded crystals with tetrabutylammonium halides and of the cyclic trimer as solvent-containing crystals was achieved. The solid-state structures of these compounds were unambiguously clarified by single crystal X-ray diffraction analysis and also by neutron diffraction study for orthosilicic acid. Based on these results, we also succeeded in developing a more practical synthetic procedure for high concentrations of stable orthosilicic acid stably in organic solvents via a simple hydrolysis of tetraalkoxysilanes.