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

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(Bu-t)(3). The TOTA(+)-P(Bu-t)(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]center dot[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.

Automated summary

The reactivity between the Lewis acidic trioxatriangulenium ion (TOTA(+)) and various Lewis bases was studied, showing different outcomes such as Lewis acid-base adducts and frustrated Lewis pairs (FLPs). The interaction was characterized through various techniques including VT NMR, X-ray diffraction, UV-visible spectroscopy, and DFT calculations. The results suggest a complex behavior between TOTA(+) and different bases, with potential applications in various organic transformations.