A new series of nitro‐substituted bis(imino)pyridine ligands {2,6‐bis[1‐(2‐methyl‐4‐nitrophenylimino)ethyl]pyridine, 2,6‐bis[1‐(4‐nitrophenylimino)ethyl]pyridine, (1‐{6‐[1‐(4‐nitro‐phenylimino)‐ethyl]‐pyridin‐2‐yl}‐ethylidene)‐(2,4,6‐trimethyl‐phenyl)‐amine, and 2,6‐bis[1‐(2‐methyl‐3‐nitrophenylimino)ethyl]pyridine} and their corresponding Fe(II) complexes [{p‐NO2o‐MePhNC(Me)PyC(Me)NPho‐ Mep‐NO2}FeCl2 (10), L2FeCl2 (11), {m‐NO2o‐MePhNC(Me)PyC(Me)NPho‐Mem‐NO2}FeCl2 (12), and {p‐NO2PhNC(Me)PyC(Me)NMes}FeCl2 (14)] were synthesized. According to X‐ray analysis, there were shortenings of the axial FeN bond lengths (up to 0.014 Å) in para‐nitro‐substituted complex 10 and (up to 0.015 Å) in meta‐nitro‐substituted complex 12 versus the Fe(II) complex without nitro groups [{o‐MePhNC(Me)PyC(Me)NPho‐Me}FeCl2 (1)]. Complexes 10, 12, and 14 afforded very active catalysts for the production of α‐olefins and were more temperature‐stable and had longer lifetimes than parent non‐nitro‐substituted Fe(II) complex 1. The reaction between FeCl2 and a sterically less hindered ligand [p‐NO2PhNC(Me)PyC(Me)NPhp‐NO2] resulted in the formation of octahedral complex 11. A para‐dialkylamino‐substituted bis(imino)pyridine ligand [p‐NEt2o‐MePhNC(Me)PyC(Me)NPho‐Mep‐NEt2] and the corresponding Fe(II) complex [{p‐NEt2o‐MePhNC(Me)PyC(Me)NPho‐Mep‐NEt2}FeCl2 (16)] were synthesized to evaluate the effect of enhanced electron donation of the ligand on the catalytic performance. According to X‐ray analysis, there was a shortening (up to 0.043 Å) of the axial FeN bond lengths in para‐diethylamino‐substituted complex 16 in comparison with parent Fe(II) complex 1. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2615–2635, 2006