Controlling selectivity in alkene oxidation and CO2 cycloaddition reactions: fine tuning of Pc-L transition metal complexes

Sustainable synthesis and green chemistry have become a fundamental tool when planning a new process. In catalysis this means to correctly design since the beginning the properties of the target metal complex. The cost and the availability of the metal ion, as well as its biocompatibility must be taken into account. Despite the fact that their greater reactivity makes more difficult their use, first row transition metals are to be considered as the first choice to plan a new catalytic cycle. In this lecture, I will provide a perspective on the catalytic applications of iron(III) and zinc(II) metal complexes of tetraaza 12-membered pyridine containing macrocyclic ligands.1 I will focus on the selective iron(III) catalysed epoxidation or dihydroxylation of alkenes by using hydrogen peroxide as terminal oxidant.2 Depending on the anion of the iron(III) metal complex employed as catalyst, a completely reversed selectivity was observed (Figure). Our approach towards the selective oxidation of alcohols by using the same catalytic system will also be covered. As for iron, catalytic applications of zinc complexes fall in the scientific community’s effort to develop more eco-friendly chemical processes. CO2 is the principal greenhouse gas, largely recognized as responsible for global warming, but it is also an abundant C1 source. Limiting CO2 emissions can only stem the problem but to solve it a circular economy based on carbon dioxide should be pursued and in this respect, research in the last decade has focussed on the design of systems able to promote the functionalisation of CO2. I will outline our approach towards the synthesis of cyclic carbonates by cycloaddition of CO2 to epoxides by using zinc(II) complexes.