Methane BeryllationCatalyzed 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.