Towards robust alkane oxidation catalysts: electronic variations in non-heme iron(ii) complexes and their effect in catalytic alkane oxidation.

A series of non-heme iron(ii) bis(triflate) complexes containing linear and tripodal tetradentate ligands has been prepared. Electron withdrawing and electron donating substituents in the para position of the pyridine ligands as well as the effect of pyrazine versus pyridine and sulfur or oxygen donors instead of nitrogen donors have been investigated. The electronic effects induced by these substituents influence the strength of the ligand field. UV-vis spectroscopy and magnetic susceptibility studies have been used to quantify these effects and VT (1)H and (19)F NMR spectroscopy as well as X-ray diffraction have been used to elucidate structural and geometrical aspects of these complexes. The catalytic properties of the iron(ii) complexes as catalysts for the oxidation of cyclohexane with hydrogen peroxide have been evaluated. In the strongly oxidising environment required to oxidise alkanes, catalyst stability determines the overall catalytic efficiency of a given catalyst, which can be related to the ligand field strength and the basicity of the ligand and its propensity to undergo oxidation.