Methane Beryllation Catalyzed by a Base Metal Complex

The homogeneous catalytic functionalization of methane is extremely challenging due to the relative nonpolarity and high C-H bond strength of this hydrocarbon. Here, using catalytic quantities (10 mol %) of CpMn(CO)₃ or Cp*Re(CO)₃, the conversion of methane and benzene C-H bonds to C-Be and H-Be bonds by CpBeBeCp has been achieved under photochemical conditions. Possible intermediates in the beryllation reactions─<i>trans</i>-bis(beryllyl)-manganese and -rhenium complexes─were also isolated. Quantum chemical calculations indicate that the inherent properties of the beryllyl ligands─which are powerfully σ-donating and feature highly Lewis acidic beryllium centers─are decisive in enabling methane functionalization by these systems.