A novel iron porphyrin complex with hydroquinone moieties as proton/electron mediators at positions was designed and synthesised. The complex serves as an efficient catalyst for photochemical CO reduction, and its turnover frequency (TOF = 1.3 × 10 h) was the highest among those of comparable systems with sufficient durability.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/d3cc01862h | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Isocyanide Ligation Enables Electrochemical Ammonia Formation in a Synthetic Cycle for N Fixation.
J Am Chem Soc
December 2024
Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
Article Synopsis
- The study focuses on using transition metals, specifically rhenium, to split nitrogen (N) and form metal nitride complexes, which could lead to efficient electrochemical nitrogen fixation to create ammonia under mild conditions.
- The proposed nitrogen fixation cycle involves binding N to form a complex, cleaving the N bridge, and then undergoing proton/electron transfer to produce ammonia, while a catalyst must fulfill specific electronic requirements during these processes.
- The introduction of an isocyanide ligand in the rhenium system helps facilitate electron reduction and protonation, increasing the stability of the process and enabling ammonia production, demonstrating how modifying supporting ligands can improve reactivity in synthetic cycles for nitrogen conversion.
Mechanistic studies of NO reduction reactions involving copper complexes: encouragement of DFT calculations.
Dalton Trans
December 2024
Institute for Materials Chemistry and Engineering and IRCCS, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan.
The reduction of nitrogen oxides (NO), which is mainly mediated by metalloenzymes and metal complexes, is a critical process in the nitrogen cycle and environmental remediation. This Frontier article highlights the importance of density functional theory (DFT) calculations to gain mechanistic insights into nitrite (NO) and nitric oxide (NO) reduction reactions facilitated by copper complexes by focusing on two key processes: the reduction of NO to NO by a monocopper complex, with special emphasis on the concerted proton-electron transfer, and the reduction of NO to NO by a dicopper complex, which involves N-N bond formation, NO isomerization, and N-O bond cleavage. These findings underscore the utility of DFT calculations in unraveling complicated reaction mechanisms and offer a foundation for future research aimed at improving the reactivity of transition metal complexes in NO reduction reactions.
View Article and Find Full Text PDFA Carborane-Derived Proton-Coupled Electron Transfer Reagent.
J Am Chem Soc
November 2024
Division of Chemistry and Chemical Engineering, California Institute of Technology (Caltech), Pasadena, California 91125, United States.
Reagents capable of concerted proton-electron transfer (CPET) reactions can access reaction pathways with lower reaction barriers compared to stepwise pathways involving electron transfer (ET) and proton transfer (PT). To realize reductive multielectron/proton transformations involving CPET, one approach that has shown recent promise involves coupling a cobaltocene ET site with a protonated arylamine Brønsted acid PT site. This strategy colocalizes the electron/proton in a matter compatible with a CPET step and net reductive electrocatalysis.
View Article and Find Full Text PDFDeciphering Electrocatalytic Hydrogen Production in Water Through a Bioinspired Water-Stable Copper(II) Complex Adorned with (NS)-Donor Sites.
ChemSusChem
October 2024
Department of Chemistry, University of North Bengal, Darjeeling, 734013, India.
Electrocatalytic hydrogen production stands as a pivotal cornerstone in ushering the revolutionary era of the hydrogen economy. With a keen focus on emulating the significance of hydrogenase-like active sites in sustainable H generation, a meticulously designed and water-stable copper(II) complex, [Cl-Cu-L]ClO, featuring the N,S-type ligand, L (2,2'-((butane-2,3-diylbis(sulfanediyl))bis(methylene))dipyridine), has been crafted and assessed for its prowess in electrocatalytic H production in water, leveraging acetic acid as a proton source. The molecular catalyst, adopting a square pyramidal coordination geometry, undergoes -Cl substitution by HO during electrochemical conditions yielding [HO-Cu-L] as the true catalyst, showcases outstanding activity in electrochemical proton reduction in acidic water, achieving an impressive rate of 241.
View Article and Find Full Text PDFMolecular Iridium Catalyzed Electrochemical Formic Acid Oxidation: Mechanistic Insights.
Angew Chem Int Ed Engl
January 2025
National Synchrotron Radiation Laboratory, Free Electron Laser for Innovation Center of Energy Chemistry (FELiChEM), CAS Center for Excellence in Nanoscience, Key Laboratory of Precision and Intelligent Chemistry, School of Nuclear Science and Technology, University of Science and Technology of China, 230029, Hefei, China.
Electrochemical formic acid oxidation reaction (FAOR) is a pivotal model for understanding organic fuel oxidation and advancing sustainable energy technologies. Here, we present mechanistic insights into a novel molecular-like iridium catalyst (Ir-N-C) for FAOR. Our studies reveal that isolated sites facilitate a preferential dehydrogenation pathway, circumventing catalyst poisoning and exhibiting high inherent activity.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!