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The rich redox chemistry of iron complexes makes them exceptionally versatile in reactions with radical or radical-forming species. Also in nature, most redox processes such as the oxidation of organic molecules are performed by iron-containing enzymes, inspiring chemists to understant, harness and replicate their reactivity with simple synthetic models.
We aim to design bioinspired iron catalysts for the sustainable and selective oxidation and amination of organic molecules. Mechanistic unnderstanding of the O-O and N-O bond activation of oxidizing (peroxides, dioxygen) and aminating reagents (hydroxylamine-derived reactants) is the cornerstone of the rational design and improvement of their structures.
Iron-mediated amination
Iron-mediated amination
Amine groups are ubiquitous in medicinally and agrochemically relevant compounds as well as in materials. However, insertion of NH2, NHR or NR2 groups currently involves multistep reactions and polluting catalysts that produce toxic wastes.
Direct amination of C-H bonds is a more straightforward and sustainable-by-design alternative, especially if non-toxic iron catalysts and readily available hydroxylamine-derived reactants are used. Unfortunately, this chemistry is still in its infancy. Applying a mechanistic approach, we aim to rationally design effective iron catalysts for the sustainable and selective amination of organic molecules and materials.
Representative publications
Homogeneous iron catalyzed C—H amination
D. Possenti, G. Olivo*, ChemCatChem 2024, 16, e202400353
more coming soon...
Iron catalyzed oxidation
Iron catalyzed oxidation
Simple iron coordination complexes act as minimalistic models of iron oxygenases and catalyze challenging oxidation of organic molecules, including the stereoselective hydroxylation of aliphatic C-H bonds. These complexes mirror the enzymatic mechanism of action, with a reactive high-valent iron (or manganese) oxo species formed after O-O bond activation of teh oxidant.
We aim to understand how the oxidant (peroxides, dioxygen) is activated at the iron centre in order to design effective and selective oxidation processes. We are also interested in rationalizing and exploiting proximity effects to replicate elusive aspects of enzymatic reactivity, from ligand rebound to oxidant activation (see also Supramolecular control of bioinspired oxidations).
Representative publications
Proximity Effects on the Reactivity of a Nonheme Iron (IV) Oxo Complex in C-H Oxidation
A. Fagnano, F. Frateloreto, R. Paoloni, C. Sappino, O. Lanzalunga, M. Costas,* S. Di Stefano,* G. Olivo,* Angew. Chem. Int. Ed. 2024, 63, e202401694.
L. Vicens, G. Olivo*, M. Costas*, Angew. Chem. Int. Ed. 2022, 61, e202114932
more coming soon...
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