Abstract
Low-valent silicon compounds such as neutral silylenes display versatile reactivity for the activation of small molecules. In contrast, their anionic congeners silanides ([R3Si−]) have primarily been investigated for their nucleophilic reactivity. Here we show that incorporating a silanide center in a bicyclic cage structure allows for formal oxidative addition of polar element-hydrogen bonds (RX−H, R=aromatic residue, X=O, S, NH). The resulting hydrosilicates were isolated and characterized structurally and spectroscopically. Density Functional Theory (DFT) calculations and experimental observations support an ionic mechanism for RX−H bond activation. Finally, the reactivity of the RS−H bond adduct was further investigated, revealing that it behaves as a Lewis pair upon facile heterolytic cleavage of the Si−S bond.
| Original language | English |
|---|---|
| Article number | e202319899 |
| Number of pages | 6 |
| Journal | Angewandte Chemie-International Edition |
| Volume | 63 |
| Issue number | 11 |
| DOIs | |
| Publication status | Published - 11 Mar 2024 |
Bibliographical note
Publisher Copyright:© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
Funding
This project has received funding from the NoNoMeCat Marie Skłodowska-Curie training network funded by the European Union under the Horizon2020 Program (675020-MSCA-ITN-2015-ETN). The X-ray diffractometer has been financed by the Netherlands Organization for Scientific Research (NWO). This work made use of the Dutch national e-infrastructure with the support of the SURF Cooperative using grants no. EINF-1254 and EINF-3520. The authors thank Prof. R. J. M. Klein Gebbink, Dr. Ing. D. L. J. Broere, and Dr. A. Thevenon for insightful comments. The authors thank C. Zagone for assistance with the design of the TOC graphic. This project has received funding from the NoNoMeCat Marie Skłodowska‐Curie training network funded by the European Union under the Horizon2020 Program (675020‐MSCA‐ITN‐2015‐ETN). The X‐ray diffractometer has been financed by the Netherlands Organization for Scientific Research (NWO). This work made use of the Dutch national e‐infrastructure with the support of the SURF Cooperative using grants no. EINF‐1254 and EINF‐3520. The authors thank Prof. R. J. M. Klein Gebbink, Dr. Ing. D. L. J. Broere, and Dr. A. Thevenon for insightful comments. The authors thank C. Zagone for assistance with the design of the TOC graphic.
| Funders | Funder number |
|---|---|
| NoNoMeCat Marie Skłodowska-Curie training network | |
| SURF | EINF‐1254, EINF‐3520 |
| Horizon 2020 Framework Programme | 675020‐MSCA‐ITN‐2015‐ETN |
| European Commission | |
| Nederlandse Organisatie voor Wetenschappelijk Onderzoek |
Keywords
- Main-group compounds
- Oxidative addition
- Silanide
- Small molecule activation