Li-7 NMR spectra of DEME-TFSA [DEME = N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium; TFSA = bis(trifluoromethanesulfonypamide], EMI-TFSA (EMI = 1-ethyl-3-methylimidazolium), MPP-TFSA (MPP = N-methyl-N-propylpyridinium), DEME-PFSA [PFSA = bis(pentafluoroethanesulfonyl)amide], and DEME-HFSA [HFSA = bis(heptafluoropropanesulfonyl)amide] ionic liquid (IL) solutions containing LiX (X = TFSA, PFSA, or HFSA) and C211 (4,7,13,18-tetraoxa-1,10-diazabicyclo[8.5.5]eicosane) were measured at various temperatures. As a result, it was found that the uncomplexed Li(I) species existing as [Li(X)(2)](-) in the present ILs exchange with the complexed Li(I) ([Li . C211](+)) and that the exchange reactions proceed through the bimolecular mechanism, [Li.C211](+) [Li-star(X)(2)](-) = [Li-star . C211](+) + [Li(X)(2)](-). Kinetic parameters [k(s)/(kg m(-1) s(-1)) at 25 degrees C, Delta H double dagger/(kJ mol(-1)), Delta S double dagger/(J K-1 mol(-1))] are as follows: 5.57 x 10(-2), 69.8 +/- 0.4, and -34.9 +/- 1.0 for the DEME-TFSA system; 5.77 x 10(-2), 70.6 +/- 0.2, and 31.9 0.6 for the EMI-TFSA system, 6.13 x 10-2, 69.0 +/- 0.3, and -36.7 +/- 0.7 for the MPP-TFSA system; 1.35 x 10-1,65.2 0.5, and 43.1 1.4 for the DEME-PFSA system; 1.14 x 10-1, 64.4 0.3, and 47.1 0.6 for the DEME-HFSA system. To compare these kinetic data with those in conventional nonaqueous solvents, the exchange reactions of Li(I) between [Li .C211](+) and solvated Li(I) in N,N-dimethylformamide (DMF) and din-ethyl sulfoxide (DMSO) were also examined. These Li(I) exchange reactions were found to be independent of the concentrations of the solvated Li(I) and hence proposed to proceed through the dissociative mechanism. Kinetic parameters [ks/s(-1) at 25 degrees C, Delta H double dagger/(kJ Delta S double dagger/(J K-1 Mol(-1))] are as follows: 1.10 x 10(-2), 68.9 +/-0.2, and -51.3 +/- 0.4 for the DMF system; 1.13 x 10(-2), 76.3 +/- 0.3, and -26.3 +/- 0.8 for the DMSO system. The differences in reactivities between ILs and nonaqueous solvents were proposed to be attributed to those in the chemical forms of the uncomplexed Li(I) species, i.e., the negatively charged species ([Li(X)(2)](-)) in ILs, and the positively charged ones ([Li(solvent)(n)](+)) in nonaqueous solvents.