The reaction of [Rh{(E)-CF[double bond, length as m-dash]CHCF3}(PEt3)3] with Zn(CH3)2 results in the methylation of the alkenyl ligand to give [Rh{(E/Z)-C(CH3)[double bond, length as m-dash]CHCF3}(PEt3)3]. Variable temperature NMR studies allowed the identification of a heterobinuclear rhodium-zinc complex as an intermediate, for which the structure [Rh(CH3)(ZnCH3){(Z)-C(CH3)[double bond, length as m-dash]CHCF3}(PEt3)2] is proposed. Based on these stoichiometric reactions, unique Negishi-type catalytic cross-coupling reactions of fluorinated propenes by consecutive C-H and C-F bond activation steps at room temperature were developed. The C-H bond activation steps provide a fluorinated ligand at Rh and deliver the fluorinated product, whereas the C-F bond activation and C-C coupling occur via outer-sphere nucleophilic attack at the fluorinated alkenyl ligand.
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