A series of new bis(imino)pyridine vanadium(III) complexes was synthesized. They were tested for the homogeneous catalytic dimerization of propylene after activation with MAO. The activity and selectivity depend on the ligand structure of the corresponding organic coordination compound. The influence of PPh3 as an additive was investigated and high dependency could be observed. (C) 2010 Elsevier B.V. All rights reserved.