On the reactions of Cu(II/I)ATP complexes with methyl radicals

The CuI/IIATP react with methyl radicals to form methane and methanol, where CuIATP reacts with •CH3 in a process that is surprisingly slow. The low-rate constant of this process is attributed to the significant rearrangement of the chelating ligand required for the transient's formation. These results were corroborated by DFT calculations of the relevant compounds. The M06-2×/6–311 + g(d,p) optimized structure of the of the [H3C-CuIII-ATP]2− intermediate, demonstrating the carbon-metal σ bond between the copper ion and the methyl radical. [Display omitted] •The reactions of Cu(II/I)ATP complexes with CH3 radicals are surprisingly slow.•The slow rate constants are attributed to the rigidity of the chelating ligand.•The reaction rates are independent of the CH3 radical steady state concentration.