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January 24, 20261 citations

Silane Redistribution Catalyzed by Mes-B-TMP+ Borinium Ion.

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MWMin-Hsiung WuYLYu-Jiang LinBCBo‐An Chen

Key Points

  • To investigate the catalytic properties of [Mes-B-TMP]+ borinium ions in mediating silane redistribution and cross-coupling reactions.
  • Demonstrated aryl transfer in ArMe2SiH to produce Ar2SiMe2 and Me2SiH2 under mild conditions.
  • Extended reaction to cross-coupling with Et2SiH2 and Et3SiH.
  • Conducted computational studies to analyze the role of amino substituents in borinium ions.
  • Successfully facilitated aryl transfer reactions with good yields.
  • Established the influence of the amino substituent on boron center's Lewis acidity.
  • Showed reversible Si-H activation while preventing B-C bond cleavage.

Abstract

Borinium ions, featuring two empty p orbitals at boron, exhibit exceptional Lewis acidity but often suffer from excessive reactivity that limits their catalytic utility. In this study, we demonstrate that the arylamino borinium ion 1+ effectively mediates aryl transfer in ArMe2SiH to afford Ar2SiMe2 and Me2SiH2 under mild conditions. The reaction can also be extended to cross-coupling between ArMe2SiH and Et2SiH2/Et3SiH. Computational studies revealed that the amino substituent in 1+ plays a pivotal role in modulating the Lewis acidity of the boron center, enabling reversible Si-H activation while preventing irreversible B-C bond cleavage and catalyst decomposition. These findings highlight the potential of electronically tuned borinium ions as catalysts for activating inert substrates in organic transformations.

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Cite This Study

Wu et al. (2026) studied this question.

synapsesocial.com/papers/6974616cbb9d90c67120b38bhttps://doi.org/10.1021/acs.inorgchem.5c05711
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