On treatment with silver­(I) oxide the complex [Cp*RhCl2(κC-MeNC3H2NCH2C6F5)] undergoes 1,4-addition of rhodium and methylene to the polyfluoroaryl ring, which loses aromaticity, affording [(η5,κ2 C-C5Me4CH2C6F5CH2NC3H2NMe)­RhCl].

We report a fluorine transfer reaction in which fluorine from a perfluorinated ligand undergoes C−F bond activation and transfers to an electrophile, resulting in the formation of a new fluorinated product and dimerization of the monodefluorinated complex. Treatment of [(η 5 ,κ 2 C− C 5 Me 4 CH 2 C 6 F 5 CH 2 NC 3 H 2 NMe)−RhCl] with the organic electrophile, toluoyl chloride, resulted in the formation of a rhodium(III) metallocycle via C−F bond activation assisted defluorinative coupling. Fission of the C− F bond liberated nucleophilic fluoride, which converted acyl chloride to acyl fluoride. The overall reaction was monitored using a multivariate analysis approach in real time.

On treatment with either freshly-prepared silver nanoparticles or silver particles mechanochemically generated by stirring silver(I) oxide in dichloromethane, the complex [Cp*IrCl2(κC-MeNC3H2NCH2C6F5)] underwent a rapid and clean cyclometallation involving carbon-fluorine bond fission to afford the product [Cp*IrCl(κC 2-MeNC3H2NCH2C6F4)].

The crystal structures of 1-(2-halo-6-fluorophenylmethyl)-1-methylimidazolium bromide salts and 1-(2-trifluoromethyl-6-fluorophenylmethyl)-1-methylimidazolium bromide [MeNC 3 H 3 NCH 2 C 6 H 3 X-2-F-6] + .Br-[X = F (1), Cl (2), Br (3), I (4), CF 3 (5)] have been determined. The crystal structure of the hydrate of salt 1 contains π-π stacked imidazolium•••difluorophenyl•••difluorophenyl•••imidazolium units. Those of salts 2, 4 and 5 possess bromide•••halofluorophenyl•••halofluorophenyl•••bromide motifs comprising anion-π and π-π stacking interactions. That of salt 4 also contains bromide•••iodide halogen bonding. The crystal structure of the sesquihydrate of salt 3 possesses bromine•••halofluorophenyl•••halofluorophenyl•••bromine motifs.

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