Several allyic lithium compounds were prepared with different potential ligands tethered at C-2. These are with CH3OCH2CH2NCH3CH2-, 5 and 1-TMS 6, with (CH3)(2)NCH2CH2NCH3CH2-, 1-TMS 7, and with ((CH3)(2)NCH2CH2)(2)NCH2-, 8 and 1-TMS 9. In all these compounds Li is fully coordinated to the pendant ligand and is sited off the axis perpendicular to the allyl plane at one of the allyl termini as indicated by a combination of X-ray crystallography and NMR spectra. Compounds 5 and 8 are Li-bridged dimers as shown by X-ray crystallography and also dimeric in benzene solution as determined from freezing point determinations. Compounds 6, 7, and 9 are monomeric in THF-d(8) or diethyl ether-d(10) solution and exhibit one bond C-13(1), Li-6 scalar coupling at low temperature. Taken together the crystallographic and NMR data indicate that all of these compounds incorporate partially delocalized allylic moieties. Compounds 5 and 8 undergo fast 1,3-Li-sigmatropic shifts that are proposed to take place within low concentrations of monomers in fast equilibrium with prevalent dimers. Averaging with increasing temperature of the one-bond C-13, Li-6 coupling constant in 6, 7, and 13 provided the dynamics of bimolecular C-Li exchange with Delta H-double dagger values of 6.7, 12, and 13 kcal center dot mol(-1), respectively. Averaging of the diastereotopic N(CH3)(2) C-13 resonances of 7 is indicative of fast transfer of coordinated ligand between faces of the allyl plane Delta H-double dagger = 5.3 kcal center dot mol(-1) combined with slower inversion at nitrogen. Compound 8 exhibits similar effects. It is concluded that variation of the ligand structure changes dynamic behavior of the compounds but has little influence of their degrees of delocalization.