Details

Autor(en) / Beteiligte

• Gasevic, Thomas
• Bamberg, Marcel
• Wicke, Julius
• Bolte, Michael
• Virovets, Alexander
• Lerner, Hans‐Wolfram
• Grimme, Stefan
• Hansen, Andreas
• Wagner, Matthias
• Bursch, Markus

Titel

Confined Lewis Pairs: Investigation of the X−→Si20 Interaction in Halogen‐Encapsulating Silafulleranes

Ist Teil von

• Angewandte Chemie (International ed.), 2024-02, Vol.63 (6), p.e202314238-n/a

Auflage

International ed. in English

Ort / Verlag

Weinheim: Wiley Subscription Services, Inc

Erscheinungsjahr

2024

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• A joint theoretical and experimental study on 32 endohedral silafullerane derivatives [X@Si20Y20]− (X=F‐I; Y=F‐I, H, Me, Et) and Th ${T_h }$ ‐[Cl@Si20H12Y8]− (Y=F‐I) is presented. First, we evaluated the structure‐determining template effect of Cl− in a systematic series of concave silapolyquinane model systems. Second, we investigated the X−→Si20 interaction energy ( Eint ${E_{{\rm{int}}} }$ ) as a function of X− and Y and found the largest Eint ${E_{{\rm{int}}} }$ values for electron‐withdrawing exohedral substituents Y. Given that X− ions can be considered as Lewis bases and empty Si20Y20 clusters as Lewis acids, we classify our inseparable host–guest complexes [X@Si20Y20]− as “confined Lewis pairs”. Third, 35Cl NMR spectroscopy proved to be highly diagnostic for an experimental assessment of the Cl−→Si20 interaction as the paramagnetic shielding and, in turn, δ ${\delta }$ (35Cl) of the endohedral Cl− ion correlate inversely with Eint ${E_{{\rm{int}}} }$ . Finally, we disclose the synthesis of [PPN][Cl@Si20Y20] (Y=Me, Et, Br) and provide a thorough characterization of these new silafulleranes. A joint theoretical and experimental study on 32 endohedral silafulleranes is presented. Template effects of Cl− are investigated for the [X@Si20Y20]− complexes that are classified as “confined Lewis pairs”. The origins of the diagnostic 35Cl NMR chemical shifts are elucidated computationally. Finally, we disclose the synthesis of [PPN][Cl@Si20Y20] (Y=Me, Et, Br) including their thorough characterization.