Wang Junyi, Jia Penghui, Sun Weicheng, Wei Yuxiang, Lin Zhenyang, Ye Qing
Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, P. R. China.
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon 999077, Hong Kong.
Inorg Chem. 2022 Jun 13;61(23):8879-8886. doi: 10.1021/acs.inorgchem.2c00944. Epub 2022 Jun 1.
The iminoboryl -carboranes (MeSi)-Cb-B≡N-R (Cb = BCH, , R = SiMe; , R = Bu) have been successfully synthesized by tetrahydrofuran (THF)-promoted isomerization from the corresponding -carborane-fused aminoboriranes Cb{BN(SiMe)R} (). The synthetic protocol of the previously reported borirane was optimized. The borirane Cb{BN(SiMe)Bu} () and the iminoboranes and were fully characterized by NMR, IR, and single-crystal X-ray diffraction analyses. The borirane isomerizes more readily than . The kinetics study revealed a bimolecular mechanism between borirane and THF, which is in good agreement with the computationally proposed reaction pathway. The title compounds are thermally robust, but compound dimerized in the presence of a catalytic amount of BuNC to give the cyclodimer . Quick equilibrium between and the isonitrile adduct was observed in solution.
亚氨基硼基 - 碳硼烷（MeSi）-Cb-B≡N-R（Cb = BCH， ，R = SiMe； ，R = Bu）已通过四氢呋喃（THF）促进的相应碳硼烷稠合氨基硼杂环丙烷Cb{BN(SiMe)R}（ ）的异构化反应成功合成。优化了先前报道的硼杂环丙烷 的合成方案。硼杂环丙烷Cb{BN(SiMe)Bu}（ ）以及亚氨基硼烷 和 通过核磁共振（NMR）、红外光谱（IR）和单晶X射线衍射分析进行了全面表征。硼杂环丙烷 比 更容易异构化。动力学研究揭示了硼杂环丙烷与THF之间的双分子机制，这与计算提出的反应途径高度一致。标题化合物具有热稳定性，但化合物 在催化量的丁腈（BuNC）存在下二聚生成环二聚体 。在溶液中观察到 和异腈加合物 之间的快速平衡。
