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Synthesis and characterization of hypercoordinated silicon anions: catching intermediates of lewis base catalysis

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 bromid...

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Main Authors: Ansmann, Nils (Author) , Hartmann, Deborah (Author) , Sailer, Sonja (Author) , Erdmann, Philipp (Author) , Maskey, Rezisha (Author) , Schorpp, Marcel (Author) , Greb, Lutz (Author)
Format: Article (Journal)
Language:English
Published: 2022
In: Angewandte Chemie. International edition
Year: 2022, Volume: 61, Issue: 27, Pages: 1-7
ISSN:1521-3773
DOI:10.1002/anie.202203947
Online Access:Verlag, kostenfrei, Volltext: https://doi.org/10.1002/anie.202203947
Verlag, kostenfrei, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202203947
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Author Notes:Nils Ansmann, Deborah Hartmann, Sonja Sailer, Philipp Erdmann, Rezisha Maskey, Marcel Schorpp, and Lutz Greb

MARC

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520 |a 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. 
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