An experimental study of the mechanism for the combined CO and CH bond activation of dimethylether by bare Fe+ ions

By means of mass spectrometric experiments, a semi-quantitative potential-energy surface for the coupled CO and CH bond activation of dimethylether by gaseous Fe+ is proposed, which can account for all experimental observations made for this system. Thus, the insertion of the metal cation into the CO bond to afford the insertion species [CH3–Fe–OCH3]+ is rate determining, followed by β-hydrogen transfer to first afford the bisligated complex (CH4)Fe(CH2O)+ and then the final products Fe(CH2O)+ + CH4.