Formation of Alkanes by Aerobic Carbon–Carbon Bond Coupling Reactions Catalyzed by a Phosphovanadomolybdic Acid

The valorization of alkanes is possible via carbon–carbon coupling reactions. A series of dialkyl cobalt complexes [(RCH_2)_2Co^(III)(bpy)_2]ClO_4 (R = H, Me, Et, and Ph) were reacted with the H_5PV_2Mo_(10)O_(40) polyoxometalate as a catalyst, leading to a selective oxidative carbon–carbon bond coupling reaction. The reaction is initiated by electron transfer from [(RCH_2)_2Co^(III)(bpy)_2]^+ to H_5PV^V_2Mo_(10)O_(40) to yield an intermediate [(RCH_2)_2Co^(IV)(bpy)_2]^(2+)–H_5PV^(IV)V^VMo_(10)O_(40), as identified by a combination of EPR and X-ray photoelectron spectroscopy experiments. The reaction is catalytic with O_2 as terminal oxidant representing an aerobic C–C bond coupling reaction