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 [(RCH₂)₂Co^III(bpy)₂]­ClO₄ (R = H, Me, Et, and Ph) were reacted with the H₅PV₂Mo₁₀O₄₀ polyoxometalate as a catalyst, leading to a selective oxidative carbon–carbon bond coupling reaction. The reaction is initiated by electron transfer from [(RCH₂)₂Co^III(bpy)₂]⁺ to H₅PV^V₂Mo₁₀O₄₀ to yield an intermediate [(RCH₂)₂Co^IV(bpy)₂]²⁺–H₅PV^IVV^VMo₁₀O₄₀, as identified by a combination of EPR and X-ray photoelectron spectroscopy experiments. The reaction is catalytic with O₂ as terminal oxidant representing an aerobic C–C bond coupling reaction.