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

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 -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)] complex.

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

A comprehensive DFT investigation has been presented to predict how a carboxylate-rich macrocycle would affect the reactivity of a non-heme Fe(IV)O complex towards C-H activation. The popular non-heme iron oxo complex [Fe(O)(N4Py)], (N4Py = ,-(bis(2-pyridyl)methyl)-bis(2-pyridylmethyl)amine) (1), has been selected here as the primary compound. It is transformed to the compound [Fe(O)(Bu-P2DA)], where Bu-P2DA = -(1',1'-bis(2-pyridyl)pentyl)iminodiacetate (2) after the replacement of two pyridine donors of N4Py with carboxylate groups.

High-valent nonheme Fe(IV)O/Ru(IV)O complexes catalyze C-H activation reactivity and hydrogen tunneling: a comparative DFT investigation.

A comprehensive density functional theory investigation has been presented towards the comparison of the C-H activation reactivity between high-valent iron-oxo and ruthenium-oxo complexes. A total of four compounds, , [Ru(IV)O(tpy-dcbpy)] (1), [Fe(IV)O(tpy-dcbpy)] (1'), [Ru(IV)O(TMCS)] (2), and [Fe(IV)O(TMCS)] (2'), have been considered for this investigation. The macrocyclic ligand framework tpy(dcbpy) implies tpy = 2,2':6',2''-terpyridine, dcbpy = 5,5'-dicarboxy-2,2'-bipyridine, and TMCS is TMC with an axially tethered -SCHCH group.

Effect of the substituent on C-H activation catalyzed by a non-heme Fe(IV)O complex: a computational investigation of reactivity and hydrogen tunneling.

Density functional theory investigations were performed to address the C-H activation reactivity and the influence of quantum mechanical tunneling catalyzed by a non-heme iron(IV)-oxo complex, namely [FeOdpaq-X], where the macrocyclic ligand dpaq represents {2-[bis(pyridine-2-yl-methyl)]amino--quinolin-8-yl-acetamido}. Counter ion and solvent corrections were incorporated in the computation to avoid self-interaction error. To find the impact of the indirectly linked substituents to the central metal atom, Fe, the macrocyclic ligand dpaq was substituted at the 5-position of its quinoline moiety represented as dpaq-X and the reactivity and hydrogen tunneling were compared with the parent ligand dpaq-H.