A series of iron(II) bis(triflate) complexes containing tripodal tetradentate nitrogen ligands with pyridine and dimethylamine donors of the type [N(CH(2)Pyr)(3-n)(CH2CH2NMe2)(n)] [n = 0 (tpa, 1), n = 1 (iso-bpmen, 3), n = 2 (Me-4-benpa, 4), n = 3 (Me-6-tren, 5)] and the linear tetradentate ligand [(CH(2)Pyr)MeN(CH2CH2)NMe(CH(2)Pyr), (bpmen, 2)] has been prepared. The preferred coordination geometry of these complexes in the solid state and in CH2Cl2 solution changes from six-to five-coordinate in the order from 1 to 5. In acetonitrile, the triflate ligands of all complexes are readily displaced by acetonitrile ligands. The complex [Fe(1)(CH3CN)(2)](2+) is essentially low spin at room temperature, whereas ligands with fewer pyridine donors increase the preference for high-spin Fe(II). Both the number of pyridine donors and the spin state of the metal center strongly affect the intensity of a characteristic MLCT band around 400 nm. The catalytic properties of the complexes for the oxidation of alkanes have been evaluated, using cyclohexane as the substrate, Complexes containing ligands 1-3 are more active and selective catalysts, possibly operating via a metal-based oxidation mechanism, whereas complexes containing ligands 4 and 5 give rise to Fenton-type chemistry.