N-Heterocyclic carbenes (NHCs) are of great importance and are powerful ligands for transition metals. A new series of sterically hindered benzimidazole-based NHC ligands (LHX) (2a, 2b, 2c, 2d, 2e, 2f), silver-NHC complexes (3a, 3b, 3c, 3d, 3e, 3f) and palladium-NHC complexes (4a, 4b, 4c, 4d, 4e, 4f) have been synthesized and characterized using appropriate spectroscopic techniques. Studies have focused on the development of a more efficient catalytic system for the Suzuki coupling reaction of aryl chlorides. Catalytic performance of Pd-NHC complexes and in situ prepared Pd(OAc)(2)/LHX catalysts has been investigated for the Suzuki cross-coupling reaction under mild reaction conditions in aqueous N,N-dimethylformamide (DMF). These complexes smoothly catalyzed the Suzuki-Miyaura reactions of electron-rich and electron-poor aryl chlorides. Copyright (c) 2014 John Wiley & Sons, Ltd.