Cationic ligands - from monodentate to pincer systems.

For a long time, the small group of cationic ligands stood out as obscure systems within the general landscape of coordinative chemistry. However, this situation has started to change rapidly during the last decade, with more and more examples of metal-coordinated cationic species being reported. The growing interest in these systems is not only of purely academic nature, but also driven by accumulating evidence of their high catalytic utility.

Sulfonium Cation in the Service of π-Acid Catalysis.

While still rare, cationic ligands offer much promise as tunable electron-withdrawing ligands for π-acid catalysis. Recently, we introduced pincer-type sulfonium cations into the list of available strongly π-acidic ancillary ligands. However, the M-S bond in sulfonium complexes of these ligands was found highly labile, precluding their catalytic applications.

Effect of Internal Ligand Strain on Coordination Behavior of PSP Pincer Ligands.

Chelating ligands and most specifically pincer ligands, with their characteristic co-planar binding, usually undergo deformations upon coordination, resulting in a significant ligand strain. Such an effect on the properties of the so formed complex has rarely been explored. This study is an attempt to analyze this strain and its contribution to the overall binding energy and coordination behavior of PSP pincer ligands.

Sulfonium cations as versatile strongly π-acidic ligands.

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.