Synthesis of Organosilicon‐Based Thioether Ligand Class Showing Defined S‐Stereogenic Coordination in Crystalline Palladium(II) Complexes

Abstract

A synthesis route to aromatic organosilicon‐based thioether ligands could be established and utilised for three congeners 2. These ligands were suitable for complexation with palladium(II) chloride forming three new complexes 3. The single crystal X‐ray diffraction and temperature‐dependent 1H and 13C‐NMR analysis of 3 are presented. The elucidated solid‐state structures suggested that one pair of diastereomers is favoured in crystalline phase and is controllable by the aro­matic substituent. However, at room temperature in solution, the conformation at the sulphur atoms can fluctuate with a coalescence temperature for 1H‐NMR around 24 °C. At –31 °C, two signal sets could be observed since the inver­sion is slower than the 1H‐NMR timescale at lower tem­pe­ratures.