Synthesis of Highly Fluorinated Arene Complexes of [Rh(Chelating Phosphine)](+) Cations, and their use in Synthesis and Catalysis

The synthesis of rhodium complexes with weakly binding highly fluorinated benzene ligands is described: 1,2,3‐F(3)C(6)H(3), 1,2,3,4‐F(4)C(6)H(2) and 1,2,3,4,5‐F(5)C(6)H are shown to bind with cationic [Rh(Cy(2)P(CH(2))(x)PCy(2))](+) fragments (x=1, 2). Their structures and reactivity with alkenes, and use in catalysis for promoting the Tishchenko reaction of a simple aldehyde, are demonstrated. Key to the synthesis of these complexes is the highly concentrated reaction conditions and use of the [Al{OC(CF(3))(3)}(4)](−) anion.