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

Mateusz K. Cybulski, Ian M. Riddlestone, Mary F. Mahon, Timothy J. Woodman, Michael K. Whittlesey

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The room temperature reaction of C6F6 or C6F5H with [Ru(IEt2Me2)2(PPh3)2H¬2] (1; IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene) generated a mixture of the trans-hydride fluoride complex [Ru(IEt2Me2)2(PPh3)2HF] (2) and the bis-carbene pentafluorophenyl species [Ru(IEt2Me2)2(PPh3)(C6F5)H] (3). The formation of 3 resulted from C-H activation of C6F5H (formed from C6F6 via stoichiometric hydrodefluorination), a process which could be reversed by working under 4 atm H2. Upon heating 1 with C6F5H, the bis-phosphine derivative [Ru(IEt2Me2)(PPh3)2(C6F5)H] (4) was isolated. A more efficient route to 2 involved treatment of 1 with 0.33 eq of TREAT-HF (Et3N·3HF); excess reagent gave instead the [H2F3]- salt (5) of the known cation [Ru(IEt2Me2)2(PPh3)2H]+. Under catalytic conditions, 1 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% 1 and Et3SiH as the reductant.
Original languageEnglish
Pages (from-to)19597-19605
Number of pages9
JournalDalton Transactions
Issue number45
Early online date17 Jul 2015
Publication statusPublished - 2015


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