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Trioxatriangulenium (TOTA+) as a Robust Carbon-based Lewis Acid in Frustrated Lewis Pair Chemistry

preprint
revised on 10.10.2020 and posted on 12.10.2020 by Aslam Shaikh, Jose M Veleta, Jules Moutet, thomas Gianetti
We report the reactivity between the 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 stable 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 was found to promote the heterolytic cleavage of disulfide bonds, formaldehyde fixation, dehydrogenation of 1,4-cyclohexadiene, heterolytic cleavage of C–Br bond, and interception of Staudinger reaction intermediate. Moreover, TOTA+ and NHC was 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 condition used.

History

Email Address of Submitting Author

tgianetti@arizona.edu

Institution

University of Arizona

Country

United States

ORCID For Submitting Author

0000-0002-3892-3893

Declaration of Conflict of Interest

No conflict of interest

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