Spontaneous ion separation of the scorpionate beryllium complex, TpBeI 1 (Tp = 1-trispyrazolylborate), occurs upon treatment with THF, yielding [TpBe(thf)]I 2, which was characterized by heteronuclear NMR spectroscopy (1H, 9Be, 13C) and structurally characterized by single crystal X-ray diffraction. 2 represents a rare example of a structurally characterized monocationic beryllium complex, and to the best of our knowledge, the synthesis of 2 by a solvent-induced ion separation has previously only been observed in the reactions of beryllium dihalides with strong Lewis bases.

Syntheses and solid-state structures of diarsane Naph2As2 (Naph = 1,8-naphthalenediyl, 1) and (Naph)5Sb4Cl2 3 are reported and the σ-donor capacity of Naph2E2 (E = As 1, Sb 2) was studied in reactions with (coe)Cr(CO)5 (coe = Z-cyclooctene), yielding Naph2As2[Cr(CO )5]2 (4) and Naph2E2Cr(CO)5 (E = As 5, Sb 6). In contrast, reactions of 1 and 3 with Me2SAuCl proceed with oxidation and formation of elemental gold as well as Naph2(AsCl)2 ( 7) and [NaphSbCl2]2 8. All complexes were characterized by elemental analyses, heteronuclear ( 1 H, 13 C) NMR and FT-IR spectroscopy as well as single crystal X-ray diffraction. Intermolecular E•••π interactions (E = As, Sb), which were observed in 7 and 8, were quantified by use of density functional theory and local coupled cluster electronic structure theory calculations. These allow to assess the nature and relative importance of covalent and non-covalent interactions and illustrate how dispersion interactions change with the electronic structure of the series of compounds.

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We present the synthesis of two silyl beryllium halides HypSiBeX·(thf) (HypSi = Si(SiMe 3 ) 3 , X = Cl 2a, I 4a) and the molecular structure of 2a as determined by single crystal X-ray diffraction. Compounds 2a and 4a were characterized via multi-nuclear NMR spectroscopy ( 1 H, 9 Be, 13 C, 29 Si), and the bonding situation was further investigated using quantum chemical calculations (with the addition of further halides X = F 1b, Cl 2b, Br 3b, I 4b). The nature of the beryllium silicon bond in the context of these compounds is highlighted and discussed.The reaction of LiSi(SiMe 3 )·(thf) 2.6 with BeX 2 (X = Cl, I) in a 1:1 mixture of dry toluene/thf at 60 • C led to the formation of 2a and 4a after stirring for 16 h (Scheme 1), which was confirmed by 9 Be NMR spectroscopy. All volatiles were removed under reduced pressure, and the residue was dried for 2 h in an oil-pump vacuum. The residue was then dissolved in a small amount of dry toluene and filtrated, and the compounds were crystallized at −28 • C (yield: 2a 83%, 4a 87%). 2a and 4a were obtained as colorless crystalline solids, which dissolve easily in a number of typical coordinating (Et 2 O, THF) and non-coordinating solvents (hexane, cyclohexane, toluene) and were characterized by multi-nuclear NMR spectroscopy (

We present the reaction of a tris(pyrazolyl) beryllium scorpionate (TpBe) complex with a weakly coordinating anion (WCA), which yields the heteroleptic complex TpBeOC(CF3)31 (TpBeORF). The product 1 has been characterized by multinuclear NMR spectroscopy (1H, 9Be, 13C) and single-crystal X-ray diffraction (scXRD). Quantum chemical calculations (DFT, NPA, LOL) were performed to study the bonding nature in 1.