Theoretical study of the hydroxylation of phenols mediated by an end-on bound superoxo–copper(II) complex

Abstract

Peptidylglycine alpha-amidating monooxygenase and dopamine beta-monooxygenase are copper-containing proteins which catalyze essential hydroxylation reactions in biological systems. There are several possible mechanisms for the reductive O(2)-activation at their mononuclear copper active site. Recently, Karlin and coworkers reported on the reactivity of a copper(II)-superoxo complex which is capable of inducing the hydroxylation of phenols with incorporated oxygen atoms derived from the Cu(II)-O(2) (.-) moiety. In the present work the reaction mechanism for the abovementioned superoxo complex with phenols is studied. The pathways found are analyzed with the aim of providing some insight into the nature of the chemical and biological copper-promoted oxidative processes with 1:1 Cu(I)/O(2)-derived species.

Electrochemical and Spectroscopic Study of Mononuclear Ruthenium Water Oxidation Catalysts: A Combined Experimental and Theoretical Investigation

“…Unless stated otherwise, the geometries of the examined molecules were optimized using the OPBE functional, with the TZP (triple-ζ polarized) basis set and a small core. This GGA functional has shown good performance in describing transition-metal complexes. ,− Time-dependent density functional theory (TDDFT) excited state calculations were performed with the B3LYP functional combined with the TZP basis set . In both the geometry optimization and the TDDFT calculations, the solvation effect of water was included by means of the conductor-like screening model COSMO .…”

“…This GGA functional has shown good performance when describing transition metal complexes. 21,[50][51][52] Time dependent density functional theory (TDDFT) excited state calculations are performed with the B3LYP functional combined with the TZP basis set. 53 In both the geometry optimization and the TDDFT calculations, the solvation effect of water is included by means of the conductor-like screening model COSMO.…”

Photocatalytic Water Splitting Cycle in a Dye-Catalyst Supramolecular Complex: Ab Initio Molecular Dynamics Simulations

“…The initial geometries of all of the catalytic intermediates of the WOC–dye supramolecular complex were optimized using DFT calculations employing the OPBE exchange–correlation functional and the triple-ζ polarized Slater-type basis set . The OPBE functional was shown to be accurate in describing transition-metal complexes, including Ru-based WOCs. − In Table S2 (SI), we show a comparison between OPBE results and those obtained with the more commonly used Perdew–Burke–Ernzerhof (PBE) functional, which provides very similar results. In the geometry optimization, the continuum solvation model (COSMO , ) for water was used.…”

Introducing a closed system approach for the investigation of chemical steps involving proton and electron transfer; as illustrated by a copper-based water oxidation catalyst

“…This GGA functional has shown good performance when describing transition metal complexes. 32,[39][40][41][42] Benchmark studies of proton transfer energies with GGA functionals show that reaction barriers are underestimated by around 3 to 3.5 kcal mol -1 when compared to those calculated with highly correlated ab initio methods. 43 However, as we have argued earlier, 44 within CPMD this is likely compensated by the quantum effect error resulting from the classical treatment of proton motion.…”