Reactions of N-(1H-benzoimidazol-2-ylmethyl)-2-methoxy aniline (L1) and N-(1H-benzoimidazol-2-ylmethyl)-2-bromo aniline (L2) with either [PdC12(COD)] or [PdCIMe(COD)] afforded the neutral palladium complexes [PdCl2(L1)] (1), [PdCIMe(L1)] (2) and [PdClMe(L2] (3), respectively. Treatment of 2 and 3 with one equivalent of PPh3 in the presence of NaBAr4 (Ar =3,5-(CF3)(2)C6H3) produced the corresponding cationic species, [PdMe(L1)]BAr4 (4) and [PdMe(L2)BAr4 (5). All the palladium complexes formed active catalysts in the methoxycarbonylation of alkenes to produce linear and branched esters. The catalytic behaviour was dependent on the catalyst structure, presence of PPh3, acid promoter and alkene chain length. (C) 2015 Elsevier B.V. All rights reserved.