Abstract
Enaminoimines TbtNHC(Me)CHC(Me)NAr ( 5, Tbt = 2,4,6-[CH(SiMe 3) 2] 3C 6H 2) bearing a Tbt group were synthesized by the two steps condensation of acetylacetone with bulky amines. Enaminoimines 5 were treated with n-BuLi to give the corresponding lithium β-diketiminates, [Li{TbtNHC(Me)CHC(Me)NAr}] ( 1). The X-ray structural analysis of [Li{TbtNC(Me)CHC(Me)NMes}] ( 1c, Mes = mesityl) revealed that it is a monomeric, solvent-free lithium β-diketiminate. The equilibrium between free 1c plus THF and THF-coordinated ( 1c · thf) was investigated in detail by the determination of the association constant ( K a) in C 6D 6 at 293 K and the Job’s plot. The heavier alkali metal complexes, sodium and potassium β-diketiminates ( 6c– 9c), were prepared by the two routes. THF-coordinated [M{TbtNC(Me)CHC(Me)NMes}(thf)] ( 6c: M = Na. 7c: M = K) were prepared by the reaction of 5c (Ar = Mes) with MH (M = Na, K). Solvent-free [M{TbtNC(Me)CHC(Me)NMes}] ( 8c: M = Na. 9c: M = K) were prepared by the reaction of 1c with t-BuOM (M = Na, K).
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