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Updated: Mar 6, 2026

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Tuning Lewis Acidity by a Transannular pπ -σ* Interaction between Boron and Silicon/Germanium Atoms Supported by a
Akihito Konishi1,2, Koichi Nakaoka1, Hideto Nakajima1
1Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka, 565-0871, Japan.
Abstract:
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.
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