Fabián G. Cantú Reinhard

TL;DR: A detailed computational study on the role of spin state in the reactivity of a high-valent manganese(V)-oxo complex with para-Z-substituted thioanisole derivatives and utilize experimental evidence to distinguish between the theoretical results.

TL;DR: This work presents a detailed computational study into para-substituted thioanisole sulfoxidation by a nonheme iron(IV)-oxo complex and finds that the enthalpy of activation is reproduced well, but all methods overestimate the entropy of activation by about 50%, for which a correction factor is recommended.

TL;DR: A computational study was performed based on an active site complex of CYP OleTJE containing the heme cofactor in the substrate binding pocket and 2-methylbutyric acid as substrate and it was shown that substrate positioning determines the accessibility of the oxidizing species to the substrate and hence the regio- and chemoselectivity of the reaction.

TL;DR: A systematic gas-phase study on reactions by iron(IV)-oxo porphyrin cation radical structures with arenes confirms the experimental hypothesis of dominant aromatic over aliphatic hydroxylation and shows that the lack of an axial ligand affects theAliphatic pathways.

TL;DR: A combined spectroscopy, kinetics and computational study on aldehyde deformylation by two side-on manganese(III)-peroxo complexes with bispidine ligands finds a novel mechanism for the reaction that is initiated by a hydrogen atom abstraction reaction, which enables a keto-enol tautomerization in the substrate.