Moisture/air-stable and robust phosphine mono- and bis-ylide palladacycles as catalyst precursors were used in Suzuki and Heck cross-coupling reactions with different aryl halides including electron-rich and electron-deficient substituents. These coupling reactions could proceed smoothly in air under optimized reaction conditions (Suzuki coupling: 0.001 mol% of palladacycle, Cs2CO3 in DMF at 110 degrees C; Heck coupling: 0.001 mol% of palladacycle, K2CO3 in NMP at 130 degrees C), affording the corresponding products in mostly good to excellent yields. Filtration experiments and poisoning studies indicate that the phosphine-ylide palladacycles decompose under reaction conditions to form active Pd (0) homogeneous species. These homogenous catalysts were exhibited high catalytic activities in the presence of low catalyst loadings, providing high yields of desired products. Applications of five-member palladacycle [(P (C) over cap )PdCl2] (1) in these coupling reactions produced comparable catalytic activities of seven-member analogs [(C (C) over cap )PdCl2] (2). We found that the palladacycle complexes containing bulky, symmetrical and unsymmetrical phosphorus ylides are the active catalysts in the appropriate Suzuki and Heck cross-coupling reactions. (C) 2014 Elsevier B.V. All rights reserved.