Institut für Anorganische Chemie, Julius-Maximilians Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
Chemistry. 2009 Nov 9;15(44):12099-106. doi: 10.1002/chem.200901749.
We report on the hydroboration of 1-[bis(trimethylsilyl)amino]-2,3-diethylborirene (3) with 9-borabicyclo[3.3.1]nonane (9-BBN), which led through ring-opening to an amino(vinyl)borane. The viscous borane was subsequently converted into a crystalline borate on treatment with MeLi. Both compounds were fully characterized by multinuclear NMR spectroscopy and in case of the latter by single-crystal X-ray diffraction analysis. To elucidate the reaction mechanism of the unexpected boron-carbon bond cleavage, DFT calculations of energy minima and transition states for the hydroboration were carried out.
我们报告了 1-[双(三甲基甲硅烷基)氨基]-2,3-二乙基硼杂环戊二烯（3）与 9-硼双环[3.3.1]壬烷（9-BBN）的硼氢化反应，该反应通过开环得到氨基（乙烯基）硼烷。粘性硼烷随后在与 MeLi 处理时转化为结晶硼酸酯。这两种化合物都通过多核 NMR 光谱进行了充分的表征，对于后者还通过单晶 X 射线衍射分析进行了表征。为了阐明硼-碳键意外断裂的反应机制，我们进行了硼氢化反应的能量极小值和过渡态的 DFT 计算。
