Carbon–fluorine bond activation of perfluorinated arenes with Cp*2ZrH2

Reaction of Cp*2ZrH2 (Cp*, pentamethylcyclopentadienyl) with excess hexafluorobenzene produces a mixture of Cp*2ZrHF, C6F5H and Cp*2Zr(C6F5)H in ca. 2:1:1 ratio. Reaction of Cp*2ZrH2 with excess C6F5H produces a mixture of Cp*2ZrHF, Cp*2Zr(C6F5)H, Cp*2Zr(o-C6F4H)H, p-C6F4H2, and o-C6F4H2 with preferred ortho aromatic CF activation. Dual mechanisms are proposed for the formation of ArFH and Cp*2Zr(ArF)H species.