Abstract
The oxidative decarboxylation of the iron(II) α-hydroxy acid (mandelic acid) complex model, biomimetic of Rieske dioxygenase, has been investigated at the density functional level. The explored mechanism sheds light on the role of the α-hydroxyl group on the dioxygen activation. The potential energy surfaces have been explored in different electronic spin states. The rate-determining step of the process is the proton transfer. The oxidative decarboxylation preferentially takes place on the quintet state.
Highlights
Encouraged by the new reactions catalyzed by Rieske dioxygenases [1,3,4], sustainable mononuclear nonheme iron complexes have been proposed for bioinspired oxidation catalysis
Since the2.singlet electronic spin state of iron-dioxygen complexes lies at veryby high only the Proposed mechanism for the oxidative decarboxylation promoted theenergy, non‐heme septet, quintet and triplet potential biomimetic complex model (a). energy surfaces (PESs) have been considered
On the basis of our density functional theory investigation on the oxidative decarboxylation On the of our density functional investigation on thecan oxidative decarboxylation promoted by basis a biomimetic nonheme complex,theory the following conclusions be drawn: promoted by a biomimetic nonheme complex, the following conclusions can be drawn: 1
Summary
The employment of biomimetic catalysts considerably increased for their related high selectivity, but because they are allowed to operate in very mild conditions and they adapt to different types of substrates [1,2]. Bioinspired catalysis using peroxides or peracids for the oxidation of hydrocarbon substrates is more common and better characterized, than that based on dioxygen in catalytic oxidations, which has not been fully explored yet and the relative reaction mechanism is often unknown This last reaction path requires both electron and proton sources [5,6,7,8,9,10,11,12,13] and cosubstrate-assisted O2 molecular activation by transition metal containing complexes can be an alternative pathway [14,15,16,17,18,19] resorting to the sacrificial reductants represented a good solution [12,20].
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