Halogenated Trityl Cations as Easy-to-Access Super Electrophiles

Abstract

Herein, we present the first easy-to-access synthesis of the perfluorotrityl cation (15F+) with commercial GaCl3 and the further functionalization of the para-fluorine atoms of 15F+ via halodefluorination using trimethylsilyl halides TMSX (X = Cl, Br). This gives access to equally reactive perhalogenated trityl derivatives (p-3Cl12F+ and p-3Br12F+), which can be handled at room temperature. The impact of the para-exchange on the electronic structure is determined by NMR and UV-Vis spectroscopy. Finally, the new synthons' high hydride ion affinities are demonstrated computationally and experimentally by hydride abstraction from the short-chain, linear alkanes n-pentane and n-butane.