The diffusion behavior of Mg2+ in electrolytes is not as readily accessible as that from Li+ or Na+ utilizing PFG NMR, due to the low sensitivity, poor resolution, and rapid relaxation encountered when attempting 25Mg NMR. In MgTFSI2/DME solutions, "bound" DME (coordinating to Mg2+) and "free" DME (bulk) are distinguishable from 1H NMR. With the exchange rates between them obtained from 2D 1H EXSY NMR, we can extract the self-diffusivities of free DME and bound DME (which are equal to that of Mg2+) before the exchange occurs using PFG diffusion NMR measurements coupled with analytical formulas describing diffusion under two-site exchange. The high activation enthalpy for exhange (65-70 kJ/mol) can be explained by the structural change of bound DME as evidenced by its reduced C-H bond length. Comparison of the diffusion behaviors of Mg2+, TFSI-, DME, and Li+ reveals a relative restriction to Mg2+ diffusion that is caused by the long-range interaction between Mg2+ and solvent molecules, especially those with suppressed motions at high concentrations and low temperatures.