Rather unexpectedly, we found that the counterion structure has a significant effect on the stoichiometric addition of DME or DG ligands to bridging cation electrolytes. For example, in reaction scheme 1, the addition of 10 equivalents of DME (path c, scheme 1) or five equivalents of DG (path d, scheme 1) to a THF solution of precursor B results in the formation of novel electrolytes 3 and 4 respectively. The associated compounds 3 and 4 (isolated from electrolytes 3 and 4 via crystallization) comprise (Mg . DME/THF) 2+ and (Mg . DG/THF) 2+ cations, respectively, instead of (MgCl) + cations.