Delicious deprotonations: The scrumptiously tantalising diphenylberyllium Brønsted‐base bratwurst can be combined with an enticing selection of Brønsted‐acid sauces to result in the formation of dreamy beryllium compounds, such as an XRD‐confirmed homoleptic beryllium alkoxide and an NHC‐stabilised beryllium Grignard. More information can be found in the Research Article by M. R. Buchner and co‐workers (DOI: 10.1002/chem.202200851).

The synthesis of beryllium halide etherates and the solution behavior in benzene, dichloromethane, and chloroform was studied by NMR, IR, and Raman spectroscopy. Mononuclear units of [BeX 2(L)2] (X = Cl, Br, I; L = Et2O, thf) were identified as the favorably formed species in solution. Treatment of the mononuclear diethyl ether beryllium halide adduct with one equivalent beryllium halide formed the dinuclear compounds [BeX 2(OEt2)]2 (X = Cl, Br, I). The solid-state structures of [BeCl2(thf)2] and [BeBr2(thf)2] have been determined by single crystal X-ray diffraction analysis. [BeI2(thf)2] decomposed in all solvents. In CD2Cl2 the salt [Be(thf)4]I2 was formed, whereas in C6D6 and CDCl3, BeI2 precipitated and [BeI(thf)3]+, [Be(thf)4]2+ together with the thf ring-opening product [Be(μ 2-O(CH2)4I)I(thf)]2 were observed in solution.

The diphenylphosphinites [(THF)Li(OPPh2)]4 and [(THF)2Be(OPPh2)2] have been synthesized via direct deprotonation of diphenylphosphine oxide with n BuLi and BePh2, respectively, as well as via salt metathesis. These compounds were characterized by multinuclear NMR spectroscopy, and the side-products of the reactions obtained under various reaction conditions have been identified. The beryllium derivative could not be isolated and decomposed into diphosphine oxide Ph2PP(O)Ph2. The solid-state structure of this final product together with that of [(THF)Li(OPPh2)]4 have been determined by single-crystal X-ray diffraction.

The reactions of beryllium halides with diphenyl beryllium were investigated in the N‐ and O‐donor solvents NEt3 and THF, as well as in benzene and dichloromethane in the presence of the Lewis basic ligands THF, NEt3 and N‐heterocyclic carbenes with various steric demand. In all cases the selective formation of heteroleptic beryllium Grignard compounds of the general formula [(L)1‐2BePhX]1‐2 (X = Cl, Br, I; L = C‐, N‐, O‐donor ligand) was observed. The stability of these complexes was investigated computationally, while the differences between homo‐ and heteroleptic systems were also evaluated NMR spectroscopically and with single crystal X‐ray diffraction. Mechanistic studies on the formation and speciation of these beryllium Grignard complexes in solution were performed.

Diphenylberyllium [Be3Ph6] is shown here to react cleanly as a Brønsted base with a vast variety of protic compounds. Through the addition of the simple molecules tBuOH, HNPh2 and HPPh2, as well as the more complex 1,3‐bis‐(2,6‐diisopropylphenyl)imidazolinium chloride, one or two phenyl groups in diphenylberyllium were protonated. As a result, the long‐postulated structures of [Be3(OtBu)6] and [Be(μ‐NPh2)Ph]2 have finally been verified and shown to be static in solution. Additionally [Be(μ‐PPh2)(HPPh2)Ph]2 was generated, which is only the second beryllium‐phospanide to be prepared; the stark differences between its behaviour and that of the analogous amide were also examined. The first crystalline example of a beryllium Grignard reagent with a non‐bulky aryl group has also been prepared; it is stabilised with an N‐heterocyclic carbene.