Palladium PEPPSI-type complexes with small NHC ligand were applied as catalyst precursors in cross coupling reactions forming a wide range of non-symmetric biaryls with high yields. The recycling of the in situ formed palladium composite was successfully performed in 10 subsequent runs. Mechanistic studies confirmed a labile character of the N-ligands coordinated to palladium by ligand exchange monitored using H-1 NMR. The formation of Pd(0) NPs during the catalytic process was evidenced by TEM. (C) 2016 Elsevier B.V. All rights reserved.