Rare Stable Fe(IV)-Superoxo Intermediate at Room Temperature

Rare Stable Fe(IV)-Superoxo Intermediate at Room Temperature

Author: ChemistryViews

Sayam Sen Gupta, Indian Institute of Science Education and Research Kolkata, Mohanpur, West Bengal, India, Jyotishman Dasgupta, Tata Institute of Fundamental Research, Mumbai, India, and colleagues have synthesized a rare yet stable Fe(IV)-superoxo intermediate at room temperature. The team first encapsulated an (Et4N)2[FeIII(Cl)(bTAML)] complex within the hydrophobic interior of a water-soluble octahedral Pd6L412+ nanocage. The dioxygen interacts with the Fe(III) site of the complex and the rare and stable Fe(IV)-superoxo intermediate is formed.

The encapsulated species were characterized through a variety of techniques including UV-vis spectroscopy, electron paramagnetic resonance (EPR), and Mössbauer spectroscopy, which collectively confirmed the presence of a stable Fe(IV)-O2•− complex inside the nanocage in water for the first time at room temerature. The cage-encapsulated complex has a short Fe–O bond distance of ∼1.70 Å. The O2 reaction is in confinement reversible, while the formed Fe(IV)-superoxo complex readily reacts when presented with substrates having weak C–H bonds, highlighting the lability of the O–O bond.

This approach provides insights into iron-based catalysis and suggests that molecular confinement could be a useful tool for studying reactive intermediates in a controlled manner. This discovery is important because it demonstrates the stabilization of a rare Fe(IV)-superoxo intermediate, which can provide insights into the reactivity and mechanisms of oxygen activation in metalloenzymes and synthetic catalysts, potentially leading to advancements in catalysis and environmental chemistry.


 

 

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