RESUMEN
The Cu-O-Cu core has been proposed as a potential site for methane oxidation in particulate methane monooxygenase. In this work, we used density functional theory (DFT) to design a mixed-valent CuIII -O-CuII species from an experimentally known peroxo-dicopper complex supported by N-donor ligands containing phenolic groups. We found that the transfer of two-protons and two-electrons from phenolic groups to peroxo-dicopper core takes place, which results to the formation of a bis-µ-hydroxo-dicopper core. The bis-µ-hydroxo-dicopper core converts to a mixed-valent CuIII -O-CuII core with the removal of a water molecule. The orbital and spin density analyses unravel the mixed-valent nature of CuIII -O-CuII . We further investigated the reactivity of this mixed-valent core for aliphatic C-H hydroxylation. Our study unveiled that mixed-valent CuIII -O-CuII core follows a hydrogen atom transfer mechanism for C-H activation. An in-situ generated water molecule plays an important role in C-H hydroxylation by acting as a proton transfer bridge between carbon and oxygen. Furthermore, to assess the relevance of a mixed-valent CuIII -O-CuII core, we investigated aliphatic C-H activation by a symmetrical CuII -O-CuII core. DFT results show that the mixed-valent CuIII -O-CuII core is more reactive toward the C-H bond than the symmetrical CuII -O-CuII core.
RESUMEN
The Cu-O-Cu core exhibits methane-to-methanol conversion, mirroring the reactivity of the copper-containing enzyme pMMO. Herein, we computationally examined the reactivity of a biomimetic Cu-O-Cu core towards methane-to-methanol conversion. The oxygen atom of the Cu-O-Cu core abstracts hydrogen present in the C-H bond of methane. The spin density at the bridging oxygen helps to abstract hydrogen from the C-H bond. We modulated the spin density of the bridging oxygen by substituting only a single copper atom of the Cu-O-Cu core by metals (M) such as Fe, Co, and Ag. These substitutions result in bimetallic [Cu-O-M]2+ models. We observed that the energy barriers for the C-H activation step and the subsequent rebound step vary with the metal M. [Cu-O-Ag]2+ exhibits the highest reactivity for M2M conversion, while [Cu-O-Fe]2+ displays the lowest reactivity. To understand the different reactivity of these models towards M2M conversion, we employed distortion-interaction analysis, orbital analysis, spin density analysis, and quantum theory of atoms in molecules analysis. Orbital analysis reveals that all four adducts follow a hydrogen atom transfer mechanism for C-H activation. Further, spin density analysis reveals that a higher spin density on the bridging oxygen leads to a lower C-H activation barrier.
RESUMEN
It has been observed in literature that the stability of tyrosinase-mimicked µ-η2 :η2 -peroxo-dicopper(II) (P) can be perturbed in presence of counter-anions (CAs) such as PhCO2 - , CF3 SO3 - , TsO- and SbF6 - . In this work, we unravel computational indicators using density functional theory to screen and study the stability of P in experimentally-reported cases. These indicators are Gibbs energies, geometrical parameters such as distances and angles, independent gradient model based on Hirshfeld partition (IGMH) generated data, orbitals' overlap, and distortion-interaction (DI) energies. Our DFT computed Gibbs energies indicate that P is stable in case of PhCO2 - and TsO- . CF3 SO3 - allows P and its isoelectronic species bis-µ-oxo-dicopper (O) to coexist. SbF6 - shows that O is in excess. Our indicators reveal that the stability of P in case of PhCO2 - and TsO- is due to the better placing of P and its CA, thus leading to better interactions and overlap of orbitals. Other indicator displays that the plane of Cu2 O2 core in P is more bend in PhCO2 - and TsO- cases as compared to the plane in the other two cases. In addition, the IGMH-based indicator displays higher values in the case of PhCO2 - and TsO- than the other CAs.
RESUMEN
A class of 2-hydroxypyridine based ligands are explored to achieve enhanced catalytic activity for ortho-C-H bond activation/arylation reaction over [(η6 -p-cymene)RuCl2 ]2 catalyst in water. Extensive studies using a series of substituted 2-hydroxypyridine based ligands (L1-L6) inferred that 5-trifluoromethyl-2-hydroxypyridine (L6) exhibited favorable effects to enhance the catalytic activity of Ru(II) catalyst for ortho C-H bond arylation of 2-phenylpyridine by 8 folds compared to those performed without ligands. The (η6 -p-cymene)Ru - L6 system also exhibited enhanced catalytic activity for ortho C-H bond arylation of 2-phenylpyridine using a variety of aryl halides. NMR and mass investigations inferred the presence of several ligand coordinated Ru(II) species, suggesting the involvement of these species in C-H bond activation reaction. Further in concurrence with the experimental findings, the density functional theory (DFT) calculations also evidenced the prominent role of 2-hydroxypyridine based ligands in Ru(II) catalyzed C-H bond arylation of 2-phenylpyridine with lower energy barrier for the C-H activation step.