Isolable fluorinated triphenylmethyl cation salts of [HCB11Cl11]-: demonstration of remarkable hydride affinity. Academic Article uri icon

abstract

  • Significantly fluorinated triarylmethyl cations have long attracted attention as potentially accessible highly reactive carbocations, but their isolation in a convenient form has proved elusive. We show that abstraction of chloride with a cationic silylium reagent leads to the facile formation of di-, tetra-, and hexafluorinated trityl cations, which could be isolated as analytically pure salts with the [HCB11Cl11]- counterion and are compatible with (halo)arene solvents. The F6Tr+ cation carrying six meta-F substituents was computationally predicted to possess up to 20% higher hydride affinity than the parent triphenylmethyl cation Tr+. We report that indeed F6Tr+ displays reactivity unmatched by Tr+. F6Tr+ at ambient temperature abstracts hydrides from the C-H bonds in tetraethylsilane, mesitylene, methylcyclohexane, and catalyzes Friedel-Crafts alkylation of arenes with ethylene, while Tr+ does none of these.

published proceedings

  • Chem Sci

altmetric score

  • 17.85

author list (cited authors)

  • Gunther, S. O., Lee, C., Song, E., Bhuvanesh, N., & Ozerov, O. V.

citation count

  • 3

complete list of authors

  • Gunther, S Olivia||Lee, Chun-I||Song, Ellen||Bhuvanesh, Nattamai||Ozerov, Oleg V

publication date

  • January 2022