Hydrogen-atom abstraction from M-E(H) to generate M═E-containing complexes (E = PR, NR) is not well studied because only a few complexes are known to undergo such reactions. Hydrogen-atom abstraction from nickel(I) phosphide and amide complexes led to the corresponding phosphinidene and imide compounds. These reactions are unparalleled in the organometallic chemistry of nickel and feature an unusual example of a transition-metal phosphinidene synthesized by hydrogen-atom abstraction.
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http://dx.doi.org/10.1021/ja107115q | DOI Listing |
J Mol Model
January 2025
Laboratorio de Química Teórica Computacional (QTC), Facultad de Química y de Farmacia, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, 7820436, Santiago de Chile, Chile.
Context: Dopamine -monooxygenase (D M) is an essential enzyme in the organism that regioselectively converts dopamine into R-norepinephrine, the key step of the reaction, studied in this paper, is a hydrogen atom transfer (HAT) from dopamine to a superoxo complex on D M, forming a hydroperoxo intermediate and dopamine radical. It was found that the formation of a hydrogen bond between dopamine and the D M catalyst strengthens the substrate-enzyme interaction and facilitates the HAT which takes place selectively to give the desired enantiomeric form of the product. Six reactions leading to the hydroperoxo intermediate were analyzed in detail using theoretical and computational tools in order to identify the most probable reaction mechanism.
View Article and Find Full Text PDFJ Phys Chem B
December 2024
Department of Chemistry and Biochemistry, Thapar Institute of Engineering and Technology, Patiala 147001, Punjab, India.
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.
View Article and Find Full Text PDFDalton Trans
December 2024
Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, Germany.
We report the proton-coupled electron transfer (PCET) reactivity of an octahedral Ta(V) aniline complex supported by an acridane-derived redox active NNN pincer ligand. The reversible binding of aniline to a Ta(V) dichloride induces significant coordination-induced bond weakening (CIBW) of the aniline N-H bonds. This enables a rare two-fold hydrogen atom abstraction, resulting in a terminal imido complex and a two-electron oxidation of the NNN pincer ligand, all while maintaining the metal's oxidation state.
View Article and Find Full Text PDFACS Omega
December 2024
N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, 47 Leninsky prosp., Moscow 119991, Russian Federation.
The electrochemically induced reaction between alkenes, bearing an allylic hydrogen atom, and -hydroxyphthalimide was investigated. Cross-dehydrogenative C-O coupling with phthalimide--oxyl radical, derived from -hydroxyphthalimide, occurs instead of oxidation of the allylic site, with the formation of a carbonyl group or functionalization of the double C=C bond. The discovered transformation proceeds in an undivided electrochemical cell equipped with a carbon felt anode and a platinum cathode.
View Article and Find Full Text PDFJ Hazard Mater
December 2024
Key Laboratory of Eco-Environments in Three Gorges Reservoir Region, Ministry of Education, College of Environment and Ecology, Chongqing University, Chongqing 400045, PR China.
Carbonate radical (CO) is inevitably produced in advanced oxidation processes (AOPs) when addressing real-world aqueous environments, yet it often goes unnoticed due to its relatively lower reactivity. In this study, we emphasized the pivotal role of CO in targeting the elimination of contaminants by contrasting it with conventional reactive oxygen species (ROSs) and assessing the removal of sulfamethazine (SMT). Similar to singlet oxygen (O), CO shows a preference for electron-rich organic compounds.
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