Unsymmetrical NCS–Pincer Palladium (II) Complexes Incorporating Pyrimidine‐Thioether–Functionalized <i>N</i> ‐Heterocyclic Carbenes: Synthesis, Structural Characterization, and Catalytic Activity in C–H Activation

ABSTRACT New unsymmetrical NCS–pincer Pd(II) complexes incorporating pyrimidine‐thioether–functionalized N ‐heterocyclic carbene (NHC) ligands were synthesized through direct metalation of imidazolium salts and subsequent anion exchange. Their structure was characterized unambiguously by NMR spectroscopy, high‐resolution mass spectrometry (HR‐MS), and single‐crystal X‐ray diffraction analysis. These complexes enabled the direct C–H arylation of challenging heteroaromatics (2‐acetylthiophene/furan and imidazole derivatives) with aryl bromides under operationally simple conditions (KOAc/DMAc), achieving excellent reactivity (yields up to 99%) and broad substrate scope.