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An in situ-generated catalytic system based on PdCl 2 and primary amine-based ligand exhibited excellent activity (up to 98% isolated yield) in the Suzuki-Miyaura cross-coupling reactions of aryl bromides with arylboronic acids in water, at room temperature, without any additive. The efficiencies of the ligands follow the order: (C 6 H 5 ) 3 CNH 2 > C 6 H 5 CH 2 NH 2 > C 6 H 5 NH 2 > C 6 H 11 NH 2 , which is in accordance with the palladacycle forming capacity of the respective ligands. Moderate-to-good yields (up to 78% isolated yield) of the coupling products were also obtained with less reactive aryl chlorides as substrates at room temperature in isopropanol using an alternative protocol based on Pd(OAc) 2 and (C 6 H 5 ) 3 CNH 2 .

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A new air‐stable Pd(II) complex containing a sulfonamide–Schiff base ligand has been synthesized, characterized and investigated as a catalyst for the Suzuki–Miyaura reactions of aryl halides with arylboronic acids. Theoretical calculations (B3LYP) and spectroscopic evidence suggest that the sulfonamide–Schiff base coordinates to the Pd centre through sulfonamide nitrogen (SO2NH2) rather than imine (CHN). The complex shows excellent cross‐coupling activity with aryl bromides in water at room temperature and aryl chlorides in isopropanol at 60°C. Copyright © 2016 John Wiley & Sons, Ltd.

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