title: 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).
abstract: 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.
authors.affiliation: Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK. m.k.whittlesey@bath.ac.uk.
authors.forename: Mateusz K
authors.initials: MK
authors.lastname: Cybulski
authors.affiliation: Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK. m.k.whittlesey@bath.ac.uk.
authors.forename: Ian M
authors.initials: IM
authors.lastname: Riddlestone
authors.affiliation: Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK. m.k.whittlesey@bath.ac.uk.
authors.forename: Mary F
authors.initials: MF
authors.lastname: Mahon
authors.affiliation: Department of Pharmacy and Pharmacology, University of Bath, Claverton Down, Bath BA2 7AY, UK.
authors.forename: Timothy J
authors.initials: TJ
authors.lastname: Woodman
authors.affiliation: Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK. m.k.whittlesey@bath.ac.uk.
authors.forename: Michael K
authors.initials: MK
authors.lastname: Whittlesey