Consequences of Correlated Solvation on the Structures and Reactivities of RLi-Diamine Complexes: 1,2-Addition and α-Lithiation Reactions of Imines by TMEDA-Solvated n-Butyllithium and Phenyllithium

6Li and 13C NMR spectroscopic studies were carried out on [6Li]n-BuLi and [6Li]PhLi (RLi) in toluene-d8 containing the following diamines:  N,N,N‘,N‘-tetramethylethylenediamine (TMEDA), N,N,N‘,N‘-tetraethylethylenediamine, 1,2-dipyrrolidinoethane, 1,2-dipiperidinoethane, N,N,N‘,N‘-tetramethylpropanediamine, trans-(R,R)-N,N,N‘,N‘-tetramethylcyclohexanediamine, and (−)-sparteine. Dimers of general structure (RLi)2S2 (S = chelating diamine) are formed in each case. Treatment of RLi with two different diamines (S and S‘) affords homosolvates (RLi)2S2 and (RLi)2S‘2 along with a heterosolvate (RLi)2SS‘. Relative binding constants and associated free energies for the sequential solvent substitutions are obtained by competing pairs of diamines. The high relative stabilities of certain heterosolvates indicate that solvent binding to the RLi dimer can be highly correlated. Rate studies of both the 1,2-addition of RLi/TMEDA to the N-isopropylimine of cyclohexane carboxaldehyde and the RLi/TMEDA-mediated α-lithiation...