Sulfonium Cation in the Service of π‐Acid Catalysis**

Abstract

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. Herein we demonstrate that this obstacle can be overcome by increasing the rigidity of the sulfonium pincer scaffold. X‐ray analyses confirm that despite bearing a formal positive charge, the sulfur atom of this newly designed sulfonium ligand maintains its coordination to the Pt(II)‐center, while DFT calculations indicate that by doing so it strongly enhances the electrophilic character of the metal. Kinetic studies carried out on three model cycloisomerization reactions prove that such a tris‐cationic sulfonium‐Pt(II) complex is highly reactive, compared to its thioether‐based analogue. This proof‐of‐concept study presents the first example of employing sulfonium‐based ligands in homogeneous catalysis.