Intramolecular C-H Oxidation in Iron(V)-oxo-carboxylato Species Relevant in the γ-Lactonization of Alkyl Carboxylic Acids.

High-valent oxoiron species have been invoked as oxidizing agents in a variety of iron-dependent oxygenases. Taking inspiration from nature, selected nonheme iron complexes have been developed as catalysts to elicit C-H oxidation through the mediation of putative oxoiron(V) species, akin to those proposed for Rieske oxygenases. The addition of carboxylic acids in these iron-catalyzed C-H oxidations has proved highly beneficial in terms of product yields and selectivities, suggesting the direct involvement of iron(V)-oxo-carboxylato species.

Unraveling the Mechanism of Hydrogen Atom Transfer by a Nickel-Hypochlorite Species and the Influence of Electronic Effects.

The oxidation of hydrocarbons is an important chemical transformation with relevance to biology and industry. Ni-catalyzed transformations are more scarce compared to Mn or Fe but have gained attention in recent years, affording efficient oxidations. Understanding the mechanism of action of these catalysts, including the detection and characterization of the active nickel-oxygen species, is of interest to design better catalysts.

Proton-triggered chemoselective halogenation of aliphatic C-H bonds with nonheme Fe-oxo complexes.

Halogenation of aliphatic C-H bonds is a chemical transformation performed in nature by mononuclear nonheme iron dependent halogenases. The mechanism involves the formation of an iron(IV)-oxo-chloride species that abstracts the hydrogen atom from the reactive C-H bond to form a carbon-centered radical that selectively reacts with the bound chloride ligand, a process commonly referred to as halide rebound. The factors that determine the halide rebound, as opposed to the reaction with the incipient hydroxide ligand, are not clearly understood and examples of well-defined iron(IV)-oxo-halide compounds competent in C-H halogenation are scarce.

Improving tobacco cessation interventions in hospitals: Pre-post evaluation of an innovative health systems intervention in Catalonia (Spain).

This study measured changes in healthcare professionals' (HCPs) performance in tobacco cessation intervention before and 6 months after a health system intervention. The intervention involved exposure to online training for staff and the implementation of a structured organizational change-level practice model that included some strategies, comprising establishing tobacco cessation steering groups with champions in each hospital, developing tailored protocols and guidelines within each organization, conducting on-site workshops for clinicians, and creating posters and pocket materials summarizing the intervention. Pre-post evaluation in four hospitals in Barcelona province (Catalonia, Spain).

Characterization of a Ferryl Flip in Electronically Tuned Nonheme Complexes. Consequences in Hydrogen Atom Transfer Reactivity.

Two oxoiron(IV) isomers ( 2a and 2b) of general formula [Fe (O)( PyNMe )(CH CN)] are obtained by reaction of their iron(II) precursor with NBu IO . The two isomers differ in the position of the oxo ligand, cis and trans to the pyridine donor. The mechanism of isomerization between 2a and 2b has been determined by kinetic and computational analyses uncovering an unprecedented path for interconversion of geometrical oxoiron(IV) isomers.