Issue 17, 2022

Sulfonium cations as versatile strongly π-acidic ligands

Abstract

More than a century old, sulfonium cations are still intriguing species in the landscape of organic chemistry. On one hand they have found broad applications in organic synthesis and materials science, but on the other hand, while isoelectronic to the ubiquitous tertiary phosphine ligands, their own coordination chemistry has been neglected for the last three decades. Here we report the synthesis and full characterization of the first Rh(I) and Pt(II) complexes of sulfonium. Moreover, for the first time, coordination of an aromatic sulfonium has been established. A thorough computational analysis of the exceptionally short S–Rh bonds obtained attests to the strongly π-accepting nature of sulfonium cations and places them among the best π-acceptor ligands available today. Our calculations also show that embedding within a pincer framework enhances their π-acidity even further. Therefore, in addition to the stability and modularity that these frameworks offer, our pincer complexes might open the way for sulfonium cations to become powerful tools in π-acid catalysis.

Graphical abstract: Sulfonium cations as versatile strongly π-acidic ligands

Supplementary files

Article information

Article type
Edge Article
Submitted
29 Jan 2022
Accepted
14 Mar 2022
First published
14 Mar 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2022,13, 4770-4778

Sulfonium cations as versatile strongly π-acidic ligands

R. Li, N. Barel, V. Subramaniyan, O. Cohen, F. Tibika and Y. Tulchinsky, Chem. Sci., 2022, 13, 4770 DOI: 10.1039/D2SC00588C

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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