Gauging ambiphilicity of pseudo-halidesviaberyllium-trispyrazolylborato compounds

Abstract

We use a series of trispyrazolylborato beryllium pseudo-halido complexes to explore the origins of the preferred isomers. A combination of experimental work together with quantum chemistry enabled an in-depth understanding of the bonding modes.

Synthesis and Derivatives of Beryllium Triflate

“…Therefore, an alternative approach was necessary, which ensured a soluble beryllium precursor with a labile solubilizing agent. Recently, SMe 2 was shown to fulfill these properties for the synthesis of beryllium pseudohalide precursors . Hence, BeCl 2 was reacted with a slight excess of TMS–OTf in SMe 2 .…”

“…Recently, SMe 2 was shown to fulfill these properties for the synthesis of beryllium pseudohalide precursors. 49 Hence, BeCl 2 was reacted with a slight excess of TMS−OTf in SMe 2 . However, initial experiments with reaction times of several days at 50 °C led to the activation of SMe 2 under the formation of [SMe 3 ] 2 [Be 2 (OTf) 6 ] (5, Figure 5).…”

Synthesis and Reactivity of Tricoordinate Organoberyllium Azides

“…[9] Given the explosion risk when heating azide compounds, the synthesis was modified recently, first performing a room-temperature chloride-azide substitution at [(Me 2 S)BeCl 2 ] 2 , followed by a salt metathesis with [(Tpb)K]. [10] While a solid-state structure of [(Tpb)BeN 3 ] was not obtained, Schulz later published the first structurally characterized homoleptic azidoberyllate, [PPh 4 ] 2 [Be(N 3 ) 4 ] (D), obtained by the reaction of [Be(N 3 ) 2 ] n with two equivalents of [PPh 4 ]N 3 . Computations suggest that the BeÀ N bonds in D should be regarded as polar-covalent (ca.…”

Synthese und Reaktivität dreifach koordinierter Organoberylliumazide

“…[9] Angesichts der Explosionsgefahr beim Erhitzen von Azidverbindungen wurde die Synthese kürzlich modifiziert, indem zunächst eine Chlorid-Azid-Substitution an [(Me 2 S)BeCl 2 ] 2 bei Raumtemperatur durchgeführt wurde, gefolgt von einer Salzmetathese mit [(Tpb)K]. [10] Während eine Festkörperstruktur von [(Tpb)BeN 3 ] nicht erhalten wurde, veröffentlichte Schulz später das erste strukturell charakterisierte homoleptische Azidoberyllat, [PPh 4 ] 2 [Be(N 3 ) 4 ] (D), das durch die Reaktion von [Be(N 3 ) 2 ] n mit zwei Äquivalenten [PPh 4 ]N 3 erhalten wurde. Berechnungen legen nahe, dass die BeÀ N-Bindungen in D als polarkovalent (ca.…”