Editorial Material
Chemistry, Multidisciplinary
Mrinalini G. Walawalkar, Priya Pandey, Ramaswamy Murugavel
Summary: The recent discoveries of dicationic and monoanionic ferrocene derivatives shed light on the impact of substituents on the C-5 ring and the selection of redox agents and solvent systems in preparing previously thought difficult synthetic targets. These oxidized and reduced forms of ferrocene are of interest to spectroscopists, magnetochemists, and theoreticians.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Weijie Yu, Shengchun Wang, Meng He, Zhou Jiang, Yi Yu, Jinping Lan, Jin Luo, Pengjie Wang, Xiaotian Qi, Tao Wang, Aiwen Lei
Summary: Introducing two similar functional groups into bulk chemical alkenes is a challenging method to synthesize complex molecules. In this study, a redox-mediated electrolysis using aryl nitriles as both aryl radical precursors and redox-mediators is demonstrated to enable intermolecular alkene 1,2-diarylation with high regioselectivity, without the need for transition-metal catalysts. This reaction utilizes cyanoarene radical anions to activate various aryl halides and produces 1,2-diarylation adducts in up to 83% yield and >20:1 regioselectivity with over 80 examples, providing a feasible approach to complex bibenzyl derivatives.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Sebastian Koniarz, Kinga Szydelko, Michal J. Bialek, Karolina Hurej, Piotr J. Chmielewski
Summary: A family of transition metal complexes based on meso-aryl-2-aza-21-carbaporphyrin (N-confused porphyrin, NCP) derivatives were synthesized and characterized. The chirality of these complexes was demonstrated by enantiomeric separation and analysis. Preliminary catalytic study showed the activity of iridium(III) ortho-metallated complexes in the N-heterocyclization of primary amines with diols.
Review
Chemistry, Multidisciplinary
Pankaj Kumar, Vyom Prakash Tyagi, Munmun Ghosh
Summary: In recent years, researchers have focused on investigating the redox properties of ancillary ligand backbones for small-molecule activation. Metal complexes have been used for the electrocatalytic H2 evolution reaction (HER), providing insights into the coupling of electrons and protons. Redox-active ligands facilitate electron transfer and promote effective orbital overlap, enabling efficient proton-coupled electron transfer reactions. Thorough spectroscopic and computational analyses are necessary for understanding catalytic mechanisms. This review summarizes recent examples of molecular electrocatalysts based on 3d transition metals and highlights the role of metal-ligand cooperativity in mechanistic pathways.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Na Chen, Zheng-Jian Wu, Hai-Chao Xu
Summary: This article highlights the innovative technique of molecular electrocatalysis in organic electrochemistry, with a specific focus on the application of ferrocene as a redox catalyst. It explores the extensive utilization of ferrocene in organic electrosynthesis, particularly emphasizing its role in the electrocatalytic generation and reactions of heteroatom- and carbon-centered radicals, among various other reactions.
ISRAEL JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Physical
Teresa Paez, FeiFei Zhang, Miguel Angel Munoz, Lara Lubian, Shibo Xi, Robert Sanz, Qing Wang, Jesus Palma, Edgar Ventosa
Summary: Different battery technologies have their own advantages and disadvantages, and by merging these technologies, a new battery technology can achieve high energy density, recyclability, and independent scalability. This new battery technology opens up previously unforeseen market opportunities, such as domestic energy storage and heavy-duty vehicle transportation.
ADVANCED ENERGY MATERIALS
(2022)
Article
Biochemistry & Molecular Biology
Hannah E. Bridgewater, Elizabeth M. Bolitho, Isolda Romero-Canelon, Peter J. Sadler, James P. C. Coverdale
Summary: Synthetic anticancer catalysts offer new approaches to low-dose therapy and targeted treatment of biochemical pathways. To optimize their activity and avoid poisoning, the synthetic organometallic redox catalyst [Os(p-cymene)(TsDPEN)] is combined with the monocarboxylate transporter (MCT) inhibitor AZD3965, which significantly increases its activity in MCF7 breast cancer cells. AZD3965 also decreases glutathione levels and enhances mitochondrial metabolism, providing a novel strategy for low-dose combination therapy.
JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Na Chen, Hai-Chao Xu
Summary: Organic radicals, versatile synthetic intermediates with complementary reactivities to ionic species, have limited scope in electrochemically driven reactions; however, research activity in organic electrochemistry has significantly increased in recent years, with the development of methods for generating and utilizing organic radicals for synthesis through direct electrolysis, molecular electrocatalysis, or molecular electrophotocatalysis.
Article
Chemistry, Multidisciplinary
Valtteri Oksanen, Sari Rautiainen, Tom Wirtanen
Summary: This study presents a nickel-bipyridine electrocatalyzed homocoupling method for synthesizing bifuran motifs, using bromine-substituted methyl furancarboxylates prepared from hemicellulose-derived furfural. The protocol utilizes sustainable carbon-based graphite electrodes in a simple setup and avoids the use of a sacrificial anode by employing triethanolamine as an electron donor. The nickel-electrocatalyzed homocoupling is applied to the preparation of bifuran-based monomers, which are isolated using precipitation.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Cesar Ruiz-Zambrana, Macarena Poyatos, Eduardo Peris
Summary: A gold complex with a naphthalene-di-imide-functionalized N-heterocyclic carbene (NHC) ligand was prepared and its reversible redox properties and catalytic activity in the hydroamination of terminal alkynes were studied.
Article
Chemistry, Multidisciplinary
Yihuan Lai, Arjun Halder, Jaehwan Kim, Thomas J. Hicks, Phillip J. Milner
Summary: In this study, it was discovered that cumulenes-organic molecules with multiple consecutive double bonds-can serve as catalytic redox mediators for the electroreductive radical borylation of inert substrates (such as electron-neutral and electron-rich aryl chlorides) at relatively mild cathodic potentials (-1.9 V vs. Ag/AgCl). This finding will guide the development of other sustainable purely electroreductive radical transformations using organic redox mediators.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Teng Yuan, Qi Tang, Chuan Shan, Xiaohan Ye, Jin Wang, Pengyi Zhao, Lukasz Wojtas, Nicholas Hadler, Hao Chen, Xiaodong Shi
Summary: This study presents a novel method for alkyne trifunctionalization through gold catalysis, achieving consecutive reactions with high efficiency and excellent yields under mild conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Haydn J. Ward, Rhys A. Ward, Nathan S. Lawrence, Jay D. Wadhawan
Summary: The study found that Ferrocenemethanol serves as a homogeneous redox mediator for hydrogen sulfide in aqueous solution, with bisulfide reacting four times faster than hydrogen sulfide. In the presence of lysed blood, higher concentrations of sulfide are required to achieve the same redox catalysis, potentially due to an interaction between Ferrocenemethanol and blood proteins.
Article
Multidisciplinary Sciences
Zohreh Hirbodvash, Oleksiy Krupin, Howard Northfield, Anthony Olivieri, Elena A. Baranova, Pierre Berini
Summary: Plasmonic catalysis has the potential to open up new reaction pathways inaccessible thermally or improve the efficiency of chemical processes. In this study, a gold stripe waveguide functioning as an electrochemical working electrode was used to propagate infrared surface plasmon polaritons (SPPs). Exciting the SPPs led to an increase in redox currents, a decrease in redox potentials correlated with photon energy, and a drop in charge transfer resistance. The observations suggest the opening of optically controlled nonequilibrium redox channels associated with energetic carrier transfer.
Review
Chemistry, Multidisciplinary
Marta Estrader, Katerina Soulantica, Bruno Chaudret
Summary: This article discusses the synthesis of magnetic metal nanoparticles using organometallic precursors, as well as their properties and potential applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Organic
Peter Schlichter, Christophe Werle
Summary: In recent years, more than 115 research publications have reported on manganese-catalyzed reducing transformations, leading to the discovery and further development of novel organometallic compounds and reduction reactions. Challenges that previously hindered the use of manganese catalysts in reduction reactions are slowly being overcome, with the hope of advancing research in this area through clear and concise overviews of catalyst structures and substrate transformations.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Johannes Nebauer, Christian Neiss, Marcel Krug, Alexander Vogel, Dominik Fehn, Shuhei Ozaki, Frank Rominger, Karsten Meyer, Kenji Kamada, Dirk M. Guldi, Andreas Goerling, Milan Kivala
Summary: This article describes a new type of nitrogen-centered polycyclic scaffold synthesized through intramolecular oxidative cyclodehydrogenation of tri(1-naphthyl)amine, which is the first example of a direct 3-fold cyclization of a triarylamine under oxidative conditions. Experimental and theoretical studies reveal the impact of cyclization on the electronic and photophysical properties, and mechanistic studies suggest the cyclization occurs under kinetic control via a dicationic mechanism.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Weiqing Mao, Dominik Fehn, Frank W. Heinemann, Andreas Scheurer, Maurice van Gastel, Sergio A. Jannuzzi, Serena DeBeer, Dominik Munz, Karsten Meyer
Summary: This study synthesized a series of cobalt complexes through oxidation reactions of the reactants, and characterized and analyzed them using experimental methods and computational methods, revealing their structures and reaction mechanisms.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Benedikt W. Grau, Alexander Neuhauser, Sadig Aghazada, Karsten Meyer, Svetlana B. Tsogoeva
Summary: Metathesis reaction is an important tool in synthetic chemistry that transforms hydrocarbon molecules through exchange of molecular fragments. There have been many modifications and improvements, including the use of iron as a catalyst.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Sascha T. Loeffler, Frank W. Heinemann, Ambre Carpentier, Laurent Maron, Karsten Meyer
Summary: In this study, a series of uranium complexes stabilized by the pentakis-benzyl-derivatized cyclopentadienyl ligand, Cp-Bn5, were reported. The complexes were synthesized by reacting [UCl4] and [UI3(1,4-dioxane)(1,5)] with the potassium salt, (CpK)-K-Bn5. The resulting complexes exhibited diverse structures and properties.
Article
Thermodynamics
Ziwen Zhai, Julius H. Jander, Alexander Bergen, Junwei Cui, Karsten Meyer, Thomas M. Koller
Summary: This study provides a strategy for determining the viscosity and surface tension of high-viscosity fluids in the form of ionic liquids (ILs) at equilibrium conditions. The combination of surface light scattering (SLS) and the pendant-drop (PD) method within one experimental setup allows for the direct evaluation of the dynamics of surface fluctuations of ILs and access to their viscosity. The reliability and self-consistency of these methods have been proven by investigating reference fluids and model ILs.
INTERNATIONAL JOURNAL OF THERMOPHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Martin Keilwerth, Weiqing Mao, Sergio A. V. Jannuzzi, Liam Grunwald, Frank W. Heinemann, Andreas Scheurer, Joerg Sutter, Serena DeBeer, Dominik Munz, Karsten Meyer
Summary: Terminal imido complexes of iron have been widely studied in metal-catalyzed nitrogen-transfer chemistry. In this study, a new tris-NHC chelating ligand (TIMMNMes) was used to synthesize and compare two series of iron alkyl imido complexes, including a reactive Fe(V) adamantyl imido intermediate. The stability and reactivity of these complexes were investigated using various characterization techniques and quantum chemical calculations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Wei-Chieh Chang, Helena Randel, Thomas Weyhermueller, Alexander A. A. Auer, Christophe Fares, Christophe Werle
Summary: In this study, a cooperative [Rh/P(O)nBu(2)] template was used for the catalytic hydrodefluorination (HDF) of perfluoroarenes under mild reaction conditions. The system showed high chemoselectivity and practicality, even in the presence of electron-donating functionalities and heterocycles. Mechanistic and theoretical studies identified a rhodium(I) dihydride complex as the catalytically relevant species and the crucial role of phosphine oxide as a cooperative fragment. Overall, this work demonstrates the potential of molecular templates for enhancing the reactivity in challenging bond activations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Judith Riedhammer, Dominik P. Halter, Karsten Meyer
Summary: This review provides a comprehensive summary of electrochemistry data reported on uranium complexes in nonaqueous electrolyte, serving as a reference for newly synthesized compounds and evaluating the influence of different ligand environments on electrochemical properties. The data for over 200 uranium compounds are reported, along with a discussion on trends observed across complexes in response to ligand field variations. The newly derived uranium-specific ligand field parameters are shown to be useful for predicting structure-reactivity correlations and activating specific substrate targets.
Article
Chemistry, Multidisciplinary
Douglas R. Hartline, Sascha T. Loeftier, Dominik Fehn, Joseph M. Kasper, Frank W. Heinemann, Ping Yang, Enrique R. Batista, Karsten Meyer
Summary: In this study, the cleavage of the O-O bond of an organic peroxide mediated by a uranium complex was investigated. This reaction proceeds via an isolable diuranium(IV/IV) intermediate and generates a stable uranium(V) bis-alkoxide complex. The significance of this research lies in the development of a new method for uranium-catalyzed O-O bond cleavage.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Weiqing Mao, Zihan Zhang, Dominik Fehn, Sergio A. V. Jannuzzi, Frank W. Heinemann, Andreas Scheurer, Maurice van Gastel, Serena DeBeer, Dominik Munz, Karsten Meyer
Summary: This study describes the synthesis, characterization, and reactivity of a series of cobalt terminal imido complexes supported by an N-anchored tripodal tris(carbene) chelate. The complexes were fully characterized using various spectroscopic and crystallographic techniques. Quantum chemical calculations provided insight into the electronic structures of the compounds. The findings highlight the reactivity of these cobalt imido complexes, including their ability to undergo intramolecular C-H bond amination and nucleophilic addition reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Andrea Squarcina, Dominik Fehn, Andreas Scheitler, Laura Senft, Alicja Franke, Achim Zahl, Ralph Puchta, Karsten Meyer, Ivana Ivanovic-Burmazovic
Summary: The most active dual superoxide dismutase (SOD) and catalase (CAT) functional analogue, the dinuclear Mn-2(II,II)L-2-core, was investigated for its catalytic O-2 (center dot-) decomposition mechanism. Two stereoisomers were studied to determine their SOD activity, characterize the intermediates involved, and differentiate between single- and di-Mn center catalysis. Structural characterization, quantum chemical analysis, and various analytical techniques supported the conclusions drawn from this study. The effects of the Mn-2(II,II)-core configuration on the SOD activity were discussed.
Article
Chemistry, Multidisciplinary
Soosan Hosseinmardi, Andreas Scheurer, Frank W. Heinemann, Nicola Marigo, Dominik Munz, Karsten Meyer
Summary: This study reports a two-step protonation reaction from a Ni-0 precursor to dihydrogen, with the formation of a rare nickel dihydrogen complex in the second protonation step.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Wowa Stroek, Martin Keilwerth, Lorraine A. Malaspina, Simon Grabowsky, Karsten Meyer, Martin Albrecht
Summary: Catalytic C-N bond formation by direct activation of C-H bonds offers wide synthetic potential. This study reports the synthesis of a stable iron alpha-N coordinated organoazide complex and reveals its reaction mechanism in solution.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Hanna H. Cramer, Shubhajit Das, Matthew D. Wodrich, Clemence Corminboeuf, Christophe Werle, Walter Leitner
Summary: This article explores the stepwise catalytic reduction of CO2 to formic acid, formaldehyde, and methanol using organometallic catalysts of earth-abundant first-row metals. A linear scaling relationship is developed to map the intrinsic reactivity of transition metal pincer complexes to their activity and selectivity in CO2 hydrosilylation. The hydride affinity of the catalysts is used to predict activity/selectivity trends, and cobalt complexes with bis(phosphino)triazine PNP-type pincer ligands exhibit outstanding properties in reaching the three reduction levels selectively. The results validate the potential of tandem computational-experimental approaches in catalyst design for CO2-based chemical transformations.
