PdII complexes with PPh(o‐C6H4SMe)2 acting as a pincer ligand in an S,S′,P‐ or S,P‐coordination mode have been synthesized. The complexes include [PdCl2{PPh(o‐C6H4SMe)2}] (1), [Pd(Me)Cl{PPh(o‐C6H4SMe)2}] (2), and [Pd(X){PPh(o‐C6H4SMe)2}]A [A = CF3SO3, X = Cl (3); A = CF3SO3, Me (4); A = PF6, X = Me (5)]. Insertion of CO into the Pd–Me bond of these complexes leads to [Pd(COMe)Cl{PPh(o‐C6H4SMe)2}] (6) and [Pd(COMe){PPh(o‐C6H4SMe)2}]A [A = CF3SO3 (7); A = PF6 (8)]. Some of these complexes are good Mizoroki–Heck catalysts (for the reactions between iodobenzene and methyl acrylate or styrene). The most active catalyst was found to be [Pd(Me)Cl{PPh(o‐C6H4SMe)2}] (2). This catalyst could be retained on a silica gel column, recovered, and reused several times without losing activity.

Palladium(II)‐complexes containing PPh(o‐C6H4SMe)2 as pincer ligand are synthesized and the complex (PDC) is utilized as highly efficient and recyclable catalyst for the Mizoroki—Heck reaction of iodobenzene with styrene or methyl acrylate.