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The room temperature reaction of C6F6 or C6F5H with [Ru(IEt2Me2)2(PPh3)2H2] (; IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene) generated a mixture of the trans-hydride fluoride complex [Ru(IEt2Me2)2(PPh3)2HF] () and the bis-carbene pentafluorophenyl species [Ru(IEt2Me2)2(PPh3)(C6F5)H] (). The formation of resulted from C-H activation of C6F5H (formed from C6F6via stoichiometric hydrodefluorination), a process which could be reversed by working under 4 atm H2. Upon heating with C6F5H, the bis-phosphine derivative [Ru(IEt2Me2)(PPh3)2(C6F5)H] () was isolated. A more efficient route to involved treatment of with 0.33 eq. of TREAT-HF (Et3N·3HF); excess reagent gave instead the [H2F3](-) salt () of the known cation [Ru(IEt2Me2)2(PPh3)2H](+). Under catalytic conditions, proved to be an active precursor for hydrodefluorination, converting C6F6 to a mixture of tri, di and monofluorobenzenes (TON = 37) at 363 K with 10 mol% and Et3SiH as the reductant.

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Stoichiometric and catalytic C–F bond activation by the trans-dihydride NHC complex [Ru(IEt2Me2)2(PPh3)2H2] (IEt2Me2= 1,3-diethyl-4,5-dimethylimidazol-2-ylidene)