Carbon–fluorine bond activation of perfluorinated arenes with Cp* 2ZrH 2

Abstract

Reaction of Cp* 2ZrH 2 (Cp*, pentamethylcyclopentadienyl) with excess hexafluorobenzene produces a mixture of Cp* 2ZrHF, C 6F 5H and Cp* 2Zr(C 6F 5)H in ca. 2:1:1 ratio. Reaction of Cp* 2ZrH 2 with excess C 6F 5H produces a mixture of Cp* 2ZrHF, Cp* 2Zr(C 6F 5)H, Cp* 2Zr( o-C 6F 4H)H, p-C 6F 4H 2, and o-C 6F 4H 2 with preferred ortho aromatic CF activation. Dual mechanisms are proposed for the formation of Ar FH and Cp* 2Zr(Ar F)H species.