Synthesis, Structure, and Computational Studies of the Tetrameric Magnesium Imides [2,4,6-Cl3C6H2NMg·S]4 (S = 1,4-Dioxane and Tetrahydrofuran)
文摘
The magnesium imide complexes [(ArNMg·diox)4·3(diox)] (4) and[(ArNMg·THF)4·tol] (5) (where Ar = 2,4,6-Cl3C6H2, diox = 1,4-dioxane, and THF = tetrahydrofuran) were prepared by theequimolar reaction of Bu2Mg with the primary amine in suitablesolvent mixtures. The successful synthesis of the halide-substitutedimides is notable because similar reactions with the less acidicorgano-substituted anilines cease upon monodeprotonation. Both4 and 5 form unusual Mg4N4 cubane aggregates in the solid state.Computational studies (HF/6-31G*) indicate that a combination ofsterics and metal solvation determines the aggregation stateadopted.