Controlling selectivity in alkene oxidation : anion driven syn-dihydroxylation or epoxidation catalysed by [Iron(III)(Pyridine-Containing Ligand)] complexes

The introduction of a pyridine moiety into the skeleton of a polyazamacrocyclic ligand affects both thermodynamic properties and coordination kinetics of the resulting metal complexes.1 These features have engendered a great interest of the scientific community. Much of the efforts in the use of macrocyclic pyridine containing ligands have been devoted to the study of catalytic oxidation reactions.2 We report here the synthesis and characterisation of [Fe(III)Pc-L’s)] complexes (Pc-L = Pyridine-Containing Ligand) and their catalytic applications in alkene oxidation reactions using H2O2 as the terminal oxidant under mild conditions (Figure). Depending on the anion employed for the synthesis of the iron(III) metal complex, we observed a completely reversed selectivity. When X = OTf, a selective syn-dihydroxylation reaction was observed. On the other hand, employing X = Cl, we obtained the epoxide as the major product. It should be pointed out that under otherwise identical reaction conditions, using FeCl3·6H2O as catalyst in the absence of the ligand, no reaction was observed.