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)2CoIII(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)2CoIII(bpy)2]+ to H5PVV2Mo10O40 to yield an intermediate [(RCH2)2CoIV(bpy)2]2+–H5PVIVVVMo10O40, 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.