New dimolybdenum complexes of composition [Mo-2{mu-Me}(2)Li(S)}(mu-X)(mu-N boolean AND N)(2)] (3a-3c), where S = THF or Et2O and N boolean AND N represents a bidentate aminopyridinate or amidinate ligand that bridges the quadruply bonded molybdenum atoms, were prepared from the reaction of the appropriate [Mo-2{mu-O2CMe}(2)(mu-N boolean AND N)(2)] precursors and LiMe. For complex 3a, X = MeCO2, while in 3b and 3c, X = Me. Solution NMR studies in C6D6 solvent support formulation of the complexes as contact ion pairs with weak agostic Mo-CH3 center dot center dot center dot Li interactions, which were also evidenced by X-ray crystallography in the solid-state structures of the molecules of 3a and 3b. Samples of 3c enriched in C-13 (99%) at the metal-bonded methyl sites were also prepared and investigated by NMR spectroscopy employing C6D6 and THF-d(8) solvents. Crystallization of 3c from toluene:tetrahydrofuran mixtures provided single crystals of the solvent separated ion pair complex [Li(THF)(4)] [Mo-2(Me)(2)(mu-Me)(mu-HC(NDipp)(2)}(2)] (4c), where Dipp stands for 2,6-iPr(2)C(6)H(3). A computational analysis of the Mo-2(mu-Me)(2)Li core of complexes 3a and 3b has been developed, which is consistent with a small but non-negligible electron-density sharing between the C and Li atoms of the mainly ionic CH3 center dot center dot center dot Li interactions.