Carbon-fluorine bond activation of perfluorinated arenes with Cp2*ZrH2

Reaction of Cp-2*ZrH2 (Cp*, pentamethylcyclopentadienyl) with excess hexafluorobenzene produces a mixture of (Cp2ZrHF)-Zr-*. C6F5H and Cp-2*Zr(C6F5)H in ca. 2:1:1 ratio. Reaction of Cp-2*ZrH2 with excess C6F5H produces a mixture of Cp-2*ZrHF. Cp-2*Zr(C6F5)H, Cp-2*Zr(o-C6F4H)H, p-C6F4H2, and o-C6F4H2 with preferred ortho aromatic C-F activation. Dual mechanisms are proposed for the formation of (ArH)-H-F and Cp-2*Zr(Ar-F)H species. (C) 2002 Elsevier Science B.V. All rights reserved.