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Frustrated Lewis Pairs Comprising Nitrogen Lewis Acids for Si–H Bond Activation
Author(s) -
Avigdori Idan,
Pogoreltsev Alla,
Kaushanski Alexander,
Fridman Natalia,
Gandelman Mark
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202008798
Subject(s) - lewis acids and bases , chemistry , frustrated lewis pair , adduct , boranes , yield (engineering) , nitrogen , silanes , polymer chemistry , medicinal chemistry , stereochemistry , organic chemistry , catalysis , boron , silane , materials science , metallurgy
N‐heterocyclic nitrogen Lewis acids are a recent addition to the field of organic chemistry. Based on nitrenium cations, these acids where previously shown to generate Lewis adducts when combined with the appropriate Lewis bases. Herein, a triazinium‐based Lewis acid was combined with t Bu 3 P to generate a frustrated Lewis pair (FLP) capable of cleaving, for the first time, Si−H bonds in silanes. Whereas low yields were initially encountered owing to insufficient Lewis acidity, a new nitrenium‐based Lewis acid was synthesized, and its superior Lewis acidity was experimentally and computationally confirmed. A FLP based on this acid cleaved the Si−H bond in PhSiH 3 , generating the triazane product in a quantitative yield. This unprecedented N−H triazane was fully characterized by multinuclear NMR techniques and single‐crystal X‐ray crystallography. A new class of compounds, N‐H triazanes display the potential capacity to participate in hydride transfer reactions.