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Issue 13, 2021
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Trioxatriangulenium (TOTA+) as a robust carbon-based Lewis acid in frustrated Lewis pair chemistry

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Abstract

We report the reactivity between the water stable Lewis acidic trioxatriangulenium ion (TOTA+) and a series of Lewis bases such as phosphines and N-heterocyclic carbene (NHC). The nature of the Lewis acid–base interaction was analyzed via variable temperature (VT) NMR spectroscopy, single-crystal X-ray diffraction, UV-visible spectroscopy, and DFT calculations. While small and strongly nucleophilic phosphines, such as PMe3, led to the formation of a Lewis acid–base adduct, frustrated Lewis pairs (FLPs) were observed for sterically hindered bases such as P(tBu)3. The TOTA+–P(tBu)3 FLP was characterized as an encounter complex, and found to promote the heterolytic cleavage of disulfide bonds, formaldehyde fixation, dehydrogenation of 1,4-cyclohexadiene, heterolytic cleavage of the C–Br bonds, and interception of Staudinger reaction intermediates. Moreover, TOTA+ and NHC were found to first undergo single-electron transfer (SET) to form [TOTA]·[NHC]˙+, which was confirmed via electron paramagnetic resonance (EPR) spectroscopy, and subsequently form a [TOTA–NHC]+ adduct or a mixture of products depending the reaction conditions used.

Graphical abstract: Trioxatriangulenium (TOTA+) as a robust carbon-based Lewis acid in frustrated Lewis pair chemistry

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Article information


Submitted
26 Oct 2020
Accepted
07 Feb 2021
First published
08 Feb 2021

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2021,12, 4841-4849
Article type
Edge Article

Trioxatriangulenium (TOTA+) as a robust carbon-based Lewis acid in frustrated Lewis pair chemistry

A. C. Shaikh, J. M. Veleta, J. Moutet and T. L. Gianetti, Chem. Sci., 2021, 12, 4841
DOI: 10.1039/D0SC05893A

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