Tuning Lewis Acidity by a Transannular pπ--σ* Interaction between Boron and Silicon/Germanium Atoms Supported by a Cage-Shaped Framework
Tuning Lewis Acidity by a Transannular pπ--σ* Interaction between Boron and Silicon/Germanium Atoms Supported by a Cage-Shaped Framework
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通过笼形框架支持的硼和硅/锗原子之间的跨环 pπ--σ* 相互作用调节路易斯酸度
DOI：
10.1002/chem.201700659
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发表时间：
2017
期刊：
影响因子：
--
通讯作者：
Makoto Yasuda
中科院分区：
文献类型：
--
作者：
Akihito Konishi;Koichi Nakaoka;Hideto Nakajima;Kouji Chiba;Akio Baba;Makoto Yasuda
合成了由较重的第14族元素（Si或Ge）束缚的笼形硼酸盐。这些化合物在硼中心和束缚的Si/Ge原子之间具有分子内跨环pπ-σ* 相互作用，这使得可以精确调节其刘易斯酸度。通过配体交换反应速率和红外光谱的测定，结合理论计算，研究了配合物的刘易斯酸性。合成的硼酸盐具有催化活性。这项研究表明，在微调刘易斯酸性的过程中，通过空间相互作用对金属中心的直接轨道扰动是有效的。
Cage‐shaped borates tethered by heavier Group 14 elements (Si or Ge) were synthesized. These possess an intramolecularly transannular pπ–σ* interaction between the boron center and the tethered Si/Ge atom, which allows the precise tuning of their Lewis acidity. The Lewis acidity was investigated by the ligand‐exchange reaction rate and IR measurements with the help of theoretical calculation. The synthesized borates exhibited catalytic activity. This study demonstrated the effectiveness of the direct orbital perturbation of a metal center by space interaction during fine tuning of the Lewis acidity.