Attempts to create a novel Mg-Be bond by reaction of [(BDI*)MgNa] with Be[N(SiMe)] failed; BDI*=HC[(tBu)C=N(DIPeP)], DIPeP=2,6-EtC-phenyl. Even at elevated temperatures, no conversion was observed. This is likely caused by strong steric shielding of the Be center. A similar reaction with the more open Cp*BeCl gave in quantitative yield (BDI*)MgBeCp* (1). The crystal structure shows a Mg-Be bond of 2.469(4) Å. Homolytic cleavage of the Mg-Be bond requires ΔH=69.6 kcal mol (cf. CpBe-BeCp 69.0 kcal mol and (BDI)Mg-Mg(BDI) 55.8 kcal mol). Natural-Population-Analysis (NPA) shows fragment charges: (BDI*)Mg +0.27/BeCp* -0.27. The very low NPA charge on Be (+0.62) compared to Mg (+1.21) and the strongly upfield Be NMR signal at -23.7 ppm are in line with considerable electron density on Be and the formal oxidation state assignment of Mg-Be. Despite this Mg-Be polarity, 1 is extremely thermally stable and unreactive towards H, CO, N, cyclohexene and carbodiimide. It reacted with benzophenone, azobenzene, phenyl acetylene, CO and CS. Reaction with 1-adamantyl azide led to reductive coupling and formation of an N-chain. The azide reagent also inserted in the Cp*-Be bond. The inertness of 1 is likely due to bulky ligands protecting the Mg-Be unit.
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