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: | , , , , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
2022
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| 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 |
| Summary: | 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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| Item Description: | Version of record online: May 5, 2022 Gesehen am 04.10.2022 |
| Physical Description: | Online Resource |
| ISSN: | 1521-3773 |
| DOI: | 10.1002/anie.202203947 |