A density functional theory analysis of the C–H activation reactivity of iron(<scp>iv</scp>)-oxo complexes with an ‘O’ substituted tetramethylcyclam macrocycle

Kaur, Lovleen; Mandal, Debasish

doi:10.1039/d4dt00063c

Dalton Trans.

2024

DOI: 10.1039/d4dt00063c

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A density functional theory analysis of the C–H activation reactivity of iron(iv)-oxo complexes with an ‘O’ substituted tetramethylcyclam macrocycle

Lovleen Kaur,

Debasish Mandal

Abstract: In this article, we present a meticulous computational study to foresee the effect of an oxygen-rich macrocycle on the reactivity of C-H activation. For this study, a widely studied nonheme...

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2024

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Computational Insights into Hydrogen Atom Transfer Mediators in C–H Activation Catalysis of Nonheme Fe(IV)O Complexes

Katoch,

Mandal

2024

J. Phys. Chem. B

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This study presents a detailed density functional theory (DFT) investigation into the mechanism and energetics of C−H activations catalyzed by bioinspired Fe(IV)O complexes, particularly in the presence of N-hydroxy mediators. The findings show that these mediators significantly enhance the reactivity of the iron-oxo complex. The study examines three substrates with varying bond dissociation energies�ethylbenzene, cyclohexane, and cyclohexadiene�alongside the [Fe(IV)O(N4Py)] 2+ complex. Mediators N-hydroxyphthalimide (NHPI) and N-hydroxyquinolinimide (NHQI) were chosen for their strong oxidative abilities. The results reveal that NO−H bond cleavage in N-hydroxy compounds occurs more readily than C−H bond cleavage in hydrocarbons, as supported by the Marcus cross-relation applied to H-abstraction. This leads to the rapid formation of aminoxyl radicals, which are more reactive than Fe(IV)O species, lowering the activation energy and enhancing the reaction rate. The C−H bond activation aligns with the Bell−Evans−Polanyi principle, correlating the activation energy with the substrate bond dissociation energy. The investigation reveals that the mediator pathway is favored both thermodynamically and kinetically. Additionally, distortion energy provides a compelling explanation for the observed reactivity trends, further highlighting NHQI's superior efficiency compared to NHPI. Additionally, quantum mechanical tunneling plays a significant role, as evidenced by the computed kinetic isotope effect, which matches experimental data.

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Computational Insights into Hydrogen Atom Transfer Mediators in C–H Activation Catalysis of Nonheme Fe(IV)O Complexes

Katoch,

Mandal

2024

J. Phys. Chem. B

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Impact of carboxylate ligation on the C–H activation reactivity of a non-heme Fe(iv)O complex: a computational investigation

Katoch,

Mandal

2024

Dalton Trans.

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A density functional theory analysis of the C–H activation reactivity of iron(iv)-oxo complexes with an ‘O’ substituted tetramethylcyclam macrocycle

Abstract: In this article, we present a meticulous computational study to foresee the effect of an oxygen-rich macrocycle on the reactivity of C-H activation. For this study, a widely studied nonheme...

Cited by 2 publications

References 64 publications

Computational Insights into Hydrogen Atom Transfer Mediators in C–H Activation Catalysis of Nonheme Fe(IV)O Complexes

Computational Insights into Hydrogen Atom Transfer Mediators in C–H Activation Catalysis of Nonheme Fe(IV)O Complexes

Impact of carboxylate ligation on the C–H activation reactivity of a non-heme Fe(iv)O complex: a computational investigation

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