C–F Bond Activation of a Perfluorinated Ligand Leading to Nucleophilic Fluorination of an Organic Electrophile

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 [(η5,κ2C–C5Me4CH2C6F5CH2NC3H2NMe)–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.