C–H and C–F bond activation reactions of pentafluorostyrene at rhodium complexes

Abstract

The rhodium(I) complexes [Rh(Bpin)(PEt₃)₃] (1), [Rh(H)(PEt₃)₃] (5) and [Rh(Me)(PEt₃)₃] (14) were employed in reactions with pentafluorostyrene affording coordination of the olefin and C–F or C–H bond activation. Control of the reaction conditions allowed for selective activation reactions at different positions at the fluorinated aromatic ring. The rhodacycle trans-[Rh(F)(CH₂CH₂(2-C₆F₄))(PEt₃)₂] (7) was identified as an intermediate for an activation at the 2-position. Reactivity studies of the latter with CO led to the generation of trans-[Rh(F)(CH₂CH₂C₆F₄)(CO)(PEt₃)₂] (10). Stoichiometric and catalytic hydroboration reactions were achieved using complexes 1 or 5 as catalysts.