Synthesis and characterization of hypercoordinated silicon anions

• Verfasst von: Ansmann, Nils [VerfasserIn]
• Verfasst von: Hartmann, Deborah [VerfasserIn]
• Verfasst von: Sailer, Sonja [VerfasserIn]
• Verfasst von: Erdmann, Philipp [VerfasserIn]
• Verfasst von: Maskey, Rezisha [VerfasserIn]
• Verfasst von: Schorpp, Marcel [VerfasserIn]
• Verfasst von: Greb, Lutz [VerfasserIn]
• Titel: Synthesis and characterization of hypercoordinated silicon anions
• Titelzusatz: catching intermediates of lewis base catalysis
• Verf.angabe: Nils Ansmann, Deborah Hartmann, Sonja Sailer, Philipp Erdmann, Rezisha Maskey, Marcel Schorpp, and Lutz Greb
• Jahr: 2022
• Umfang: 7 S.
• Fussnoten: Version of record online: May 5, 2022 ; Gesehen am 04.10.2022
• Titel Quelle: Enthalten in: Angewandte Chemie
• Ort Quelle: Weinheim : Wiley-VCH, 1962
• Jahr Quelle: 2022
• Band/Heft Quelle: 61(2022), 27, Artikel-ID e202203947, Seite 1-7
• ISSN Quelle: 1521-3773
• DOI: doi:10.1002/anie.202203947
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: Anionic Silicates
• Sach-SW: Hypercoordination
• Sach-SW: Lewis Base Catalysis
• Sach-SW: Lewis Superacid
• Sach-SW: Silicon
• K10plus-PPN: 1818010518
• K10plus-PPN:
  Universitätsbibliothek
• Lokale URL UB: Zum Volltext

Abstract

Anionic hypercoordinated silicates with weak donors were proposed as key intermediates in numerous silicon-based reactions. However, their short-lived nature rendered even spectroscopic observations highly challenging. Here, we characterize hypercoordinated silicon anions, including the first bromido-, iodido-, formato-, acetato-, triflato- and sulfato-silicates. This is enabled by a new, donor-free polymeric form of Lewis superacidic bis(perchlorocatecholato)silane 1. Spectroscopic, structural, and computational insights allow a reassessment of Gutmann's empirical rules for the role of silicon hypercoordination in synthesis and catalysis. The electronic perturbations of 1 exerted on the bound anions indicate pronounced substrate activation.