Small-Molecule Activation with Iron Porphyrins using Electrons, Photons and Protons: Some Recent Advances and Future Strategies

Substituted tetraphenyl Fe porphyrins are versatile molecular catalysts for the activation of small molecules (such as O2, H++ or CO2), which could lead to renewable energy storage, the direct production of fuels or new catalytic relevant processes. Herein, we review the recent studies of these earth-abundant metal catalysts for the electrochemical activation of dioxygen on the one hand and for the photostimulated reduction of carbon dioxide on the other hand. These two prototype reactions illustrate how mechanistic studies are the only rational approach to gain fundamental insights into the elementary steps that drive the catalysis and for identification of the key intrinsic parameters controlling the reactivity offering in turn the possibility to rationally tune the structure of the catalysts as well
as the catalytic conditions.

Substituted tetraphenyl Fe porphyrins are versatile molecular catalysts for the activation of small molecules
(such as O2, H++ or CO2), which could lead to renewable energy storage, the direct production of
fuels or new catalytic relevant processes. Herein, we review the recent studies of these earth-abundant
metal catalysts for the electrochemical activation of dioxygen on the one hand and for the photostimulated
reduction of carbon dioxide on the other hand. These two prototype reactions illustrate how
mechanistic studies are the only rational approach to gain fundamental insights into the elementary steps
that drive the catalysis and for identification of the key intrinsic parameters controlling the reactivity,
offering in turn the possibility to rationally tune the structure of the catalysts as well as the catalytic
conditions.