Abstract
Atomic partial charges are local, model-dependent descriptors that often fail to capture the global electrostatic environment governing chemical reactivity. This study demonstrates that the molecular electrostatic potential (ESP) at the Si–H hydrogen in trisubstituted silanes reliably predicts electrophilic versus nucleophilic behavior, whereas local charges alone can mislead. Electron-donating substituents generate hydridic hydrogens with negative ESP near hydrogen, favoring nucleophilicity. Electron-withdrawing substituents typically leave hydrogen with a negative local charge but generate a positive ESP region along the Si–H axis, promoting electrophilic character. Increasing solvent polarity amplifies these contrasts, driving minima more negative for electron-donating substituents and maxima more positive for electron-withdrawing substituents. The resulting positive region near hydrogen in electron-withdrawing silanes is directionally σ-hole-like, yet unlike classical σ-holes from lone-pair depletion, it reflects a collective molecular electrostatic effect. These findings highlight the importance of global electrostatics for understanding structure–reactivity relationships and predicting substituent-controlled behavior in silicon hydrides.
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The data that support the findings of this study are available in the supporting information of this article. The publication data are available at ZENODO https://doi.org/10.5281/zenodo.18852906 under the same title.
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Acknowledgements
This article has been produced with the financial support of the European Union under the REFRESH – Research Excellence for Region Sustainability and High-tech Industries project number CZ.10.03.01/00/22_003/0000048 via the Operational Programme Just Transition (P.H.). V.H. acknowledges the support from ERDF/ESF Project TECHSCALE (Grant CZ.02.01.01/00/22_008/0004587).
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P.H. supervised the project. R.L. and D.M. carried out the quantum chemical calculations. V.H. performed the experiments. All authors discussed the results and commented on the manuscript.
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Hrubý, V., Manna, D., Lo, R. et al. Ambiphilic behavior of hydrogen in trisubstituted silanes induced by substituent controlled polarity inversion. Commun Chem (2026). https://doi.org/10.1038/s42004-026-01980-1
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DOI: https://doi.org/10.1038/s42004-026-01980-1
