Carbon−Fluorine Bond Cleavage by Zirconium Metal Hydride Complexes

The zirconium hydride dimer [Cp 2 ZrH 2 ] 2 reacts with C 6 F 6 at ambient temperature to give Cp 2 Zr(C 6 F 5 )F as the major product along with Cp 2 ZrF 2, C 6 F 5 H and H 2 . Neither the reaction rate nor the product ratio is affected by changes in H 2 pressure or the concentration of C 6 F 6 . The reaction follows zero-order kinetics. The new compound Cp 2 Zr(C 6 F 5 )F has been structurally characterized. [Cp 2 ZrH 2 ] 2 reacts with C 6 F 5 H to give Cp 2 Zr( p -C 6 F 4 H)F, Cp 2 ZrF 2, C 6 F 4 H 2, and H 2 . The zirconium hydride Cp 3 ZrH has been structurally characterized and also reacts with C 6 F 6 . The products of the reaction are CpH, Cp 2 Zr(C 6 F 5 )F, C 6 F 5 H, Cp 2 ZrF 2, Cp 4 Zr, and Cp 3 ZrF. The reaction rate is first order in [Cp 3 ZrH] and [C 6 F 6 ], but the product ratio is unaffected by the concentration of C 6 F 6 . Possible mechanisms of these reactions are discussed.