Proton, C-13, Li-6, and N-15 NMR line-shape studies of exo,exo-1-trimethylsilyl-3-(dimethylethylsilyl)-allyllithium-Li-6 complexed to [N-14,N-15]-N,N,N',N'-tetramethylethylenediamine (TMEDA) 2 as a function of temperature and of added diamine reveal the dynamics of three fast equilibrium reorganization processes. These are (with DeltaH(double dagger) values in kilocalories per mole and DeltaS(double dagger) values in entropic units): mutual exchange of lithium between two 2 molecules (6.3, -21), exchange of TMEDA between its free and complexed states (5.0 and -22), and first-order transfer of complexed ligand between the allyl faces (7.0 and -20). Intermediates that are dimeric in TMEDA are proposed for the first two of these reorganization processes.