Several benzofurobenzofuran and methanodibenzodioxocine iminopyridine derivatives have been used as ligands to form mononuclear and dinuclear iron complexes. Complexes 6, 7, 8, 9 and 10 were able to promote the catalytic oxidation of benzylic C–H bonds to ketones in moderate to high yields. The effects of backbone scaffold, nuclearity (mononuclear versus dinuclear) and nitrogen hybridization (iminopyridine versus aminopyridine) were studied. A strong effect on the yields of the nature and position of the substituents in the substrates was observed.