Silylium ions can be very fleeting — so much so that their isolation was once considered impossible. This prevailing opinion was eventually challenged by chemists brave enough to conduct the challenging experiments that revealed silylium ions to not only be tractable but also synthetically versatile.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 digital issues and online access to articles
$119.00 per year
only $9.92 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
References
Walker, J. C. L., Klare, H. F. T. & Oestreich, M. Cationic silicon Lewis acids in catalysis. Nat. Rev. Chem. https://doi.org/10.1038/s41570-019-0146-7 (2020).
Reed, C. A. The silylium ion problem, R3Si+. Bridging organic and inorganic chemistry. Acc. Chem. Res. 31, 325–332 (1998).
Corey, J. Y. Generation of a silicenium ion in solution. J. Am. Chem. Soc. 97, 3237–3238 (1975).
Corey, J. Y., Gust, D. & Mislow, K. Generation of a ferrocenylsilicenium ion. J. Organomet. Chem. 107, C7–C8 (1975).
Bickart, P., Llort, F. & Mislow, K. On the evidence for the generation of a ferrocenylsilicenium. J. Organomet. Chem. 116, C1–C2 (1976).
Riddlestone, I. M. et al. Taming the cationic beast: novel developments in the synthesis and application of weakly coordinating anions. Angew. Chem. Int. Ed. 57, 13982–14024 (2018).
Müther, K. et al. A unique transition metal-stabilized silicon cation. J. Am. Chem. Soc. 133, 12442–12444 (2011).
Olah, G. A. et al. Superacid Chemistry 2nd edn Ch. 3–4 (John Wiley & Sons, 2009).
Kim, K.-C. et al. Crystallographic evidence for a free silylium ion. Science 297, 825–827 (2002).
Lambert, J. B. et al. Crystal structure of a silyl cation with no coordination to anion and distant coordination to solvent. Science 260, 1917–1918 (1993).
Shao, B. et al. Arylation of hydrocarbons enabled by organosilicon reagents and weakly coordinating anions. Science 355, 1403–1407 (2017).
Wu, Q. et al. Characterization of hydrogen-substituted silylium ions in the condensed phase. Science 365, 168–172 (2019).
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Competing interests
The author declares no competing interests.
Rights and permissions
About this article
Cite this article
Siegel, J.S. Silylium ions: from controversial beginnings to useful catalysts. Nat Rev Chem 4, 4–5 (2020). https://doi.org/10.1038/s41570-019-0151-x
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41570-019-0151-x
