The present study pretends to unravel by means of DFT calculations how the energy profile changes replacing the precious Ru or Cu by the nonprecious Fe. Different applications were faced, first for the Ru-Hbpp water oxidation catalyst. This change might remove or at least decrease the potential carcinogenic toxicity due to Ru, however computationally supposes to increase the difficulty of the right assignment of the ground state multiplicity of dinuclear iron complexes when interacting with oxygen. The reaction pathway for Fe-Hbpp arises promising results and now it is a challenge its synthesis. Another application with Fe has studied reaction mechanism proposed for the formation of oxoiron(IV) complexes starting from a non-heme reactant complexes and molecular oxygen. We also addressed the possible role of redox-inactive Sc3+. Our computational results substantially confirm the proposed mechanism and, more importantly, support that Sc3+ could trigger the molecular oxygen activation, forming a thermodynamically stable Sc3+-peroxo-Fe3+ core that facilitates O?O bond cleavage to generate the product. These insights may pave a way to improve the catalytic reactivity of metal-oxo complexes in molecular oxygen activation at non-heme centers. Finally the substitution of Ru by Fe in Grubbs catalysts demonstrated this is not a trivial transformation.1. A. Poater, Catal. Commun. 2014 , 44, 2-5

Computational hints in Fe-based catalysts

248th National Meeting (2014)

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