Article
Chemistry, Multidisciplinary
Lv-Bing Yuan, Ya-Yong Sun, Jian Zhang, Lei Zhang
Summary: A new versatile heterometallic {BiNb4} moiety has been successfully developed for the assembly of less explored organic-inorganic hybrid polyoxoniobates, showing different cluster structures formed through controlled condensation reactions under different conditions. The stepwise bottom-up assembly process of the {BiNb4} units has been confirmed using mass spectrometry, providing insights into the mechanism of condensation and recombination of metal-oxo clusters.
SCIENCE CHINA-CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Erik T. Ouellette, Julian S. Magdalenski, Robert G. Bergman, John Arnold
Summary: Low-valent transition metalates are highly reactive chemical reagents that find applications in organic synthesis, small-molecule activation, transient species stabilization, and M-E bond formation. Recent studies have discovered new types of highly reactive metalates without traditional carbonyl ligands. These metalates display unique reactivity in small-molecule activation, metal-metal bond formation, and heterometallic complex synthesis.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Organic
Abhishek Nair, Vikas Tiwari, Ashutosh Verma, Parul Saini, Anil J. Elias
Summary: In this study, a new method for synthesizing aminodiborane is reported and applied for the reduction of carboxamides. The method allows the synthesis of various amides with high yields and is also useful for preparing important pharmaceutical compounds. Control experiments and DFT studies have provided insights into the mechanistic pathway of this reaction.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Skye Fortier, Alejandra Gomez-Torres
Summary: Titanium is a versatile metal with important applications in practical synthesis, typically limited to stoichiometric reactions or Lewis acid catalysis. Interest has grown in using titanium and other early-metals for redox catalysis, but limitations exist due to their thermodynamic preference for high oxidation states. However, low-valent titanium complexes and their synthons are known, and recent developments have focused on reversible oxidative-addition/reductive-elimination reactions using these systems.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Kritika Keshari, Moumita Bera, Lucia Velasco, Sandip Munshi, Geetika Gupta, Dooshaye Moonshiram, Sayantan Paria
Summary: A terminal (FeOH)-O-III complex has been synthesized and characterized, showing the formation of a ligand radical complex in further reactions mimicking the oxygen rebound step of cytochrome P450. Kinetic analysis revealed the crucial role of a hydrogen atom transfer mechanism in the reactions.
Article
Chemistry, Inorganic & Nuclear
Florian R. Neururer, Shenyu Liu, Daniel Leitner, Marc Baltrun, Katherine R. Fisher, Holger Kopacka, Klaus Wurst, Lena J. Daumann, Dominik Munz, Stephan Hohloch
Summary: This study reports the synthesis of a vanadium(V) oxo complex with a pincer-type MIC ligand, and demonstrates that MICs are stronger donors for early transition metals with low d-electron population. The electronic and electrochemical properties were compared with a benzimidazolinylidene congener, showing reversible reduction in both vanadium(V) and vanadium(IV) oxidation states. Computational methods were used to investigate the electronic structures of the compounds. The study highlights the potential of MICs in supporting early transition-metal complexes in various oxidation states for small molecule activation and redox catalysis.
INORGANIC CHEMISTRY
(2021)
Review
Chemistry, Physical
Zahoor H. Farooqi, Robina Begum, Khalida Naseem, Weitai Wu, Ahmad Irfan
Summary: This review provides an overview of the synthesis, stabilization, and characterization of zero valent Fe nanoparticles, with a focus on their use as reducing agents and catalysts in reduction reactions. The catalytic reduction of various organic substrates using different hydrogen sources in the presence of Fe nanoparticles is critically discussed. The challenges and future perspectives in the field of iron nanoparticle-catalyzed reduction reactions are also described.
CATALYSIS REVIEWS-SCIENCE AND ENGINEERING
(2022)
Article
Chemistry, Multidisciplinary
Eugenia Miguel-Casan, Mohanad D. Darawsheh, Victor Farina-Torres, Inigo J. Vitorica-Yrezabal, Eduardo Andres-Garcia, Martin Fananas-Mastral, Guillermo Minguez Espallargas
Summary: This study successfully synthesized a stable palladium-based metal-organic framework and demonstrated its excellent catalytic activity and selectivity in the Suzuki-Miyaura allylation of aryl and alkyl boronates. This has important implications for the development of efficient catalysts.
Article
Chemistry, Multidisciplinary
Philipp Dabringhaus, Julie Willrett, Ingo Krossing
Summary: Low-valent aluminium compounds, which are highly reactive, have been widely studied in the field of chemistry. In this study, a method for synthesizing [Al(AlCp*)(3)](+)[Al(ORF)(4)](-) was reported, and it was found that the salt forms a dimer in the solid state and concentrated solutions.
Article
Chemistry, Inorganic & Nuclear
Sebastian Weiss, Max Widemann, Klaus Eichele, Hartmut Schubert, Lars Wesemann
Summary: The study shows that low valent organoelement hydrides of tin and lead react with different substrates to form hydroelementation products, with transfer of hydride to carbon atom and formation of new coordination structures.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Marti Gimferrer, Sergi Danes, Eva Vos, Cem B. Yildiz, Ines Corral, Anukul Jana, Pedro Salvador, Diego M. Andrada
Summary: This article discusses the electronic structure of Lewis base-stabilized Be and Mg compounds and provides an explanation for their proposed oxidation states. The experimentally accomplished compounds rely on increasing the π-acidity of the ligand to strengthen the chemical bonds, and it is suggested that avoiding this interaction could lead to the presence of low-oxidation states.
Article
Environmental Sciences
Youngyu Choi, Muthuraman Govindan, Daekeun Kim
Summary: The electrochemical degradation of gaseous air pollutants, such as volatile organic compounds (VOCs), is still in its early stages due to slow electron transfers at room temperature. This study proposes a triphase reaction condition using a semi-solid electrolyte layer to enhance electron transfer. By inserting a polyvinyl alcohol (PVA) gel layer between a bimetallic CuNi(CN)4 complex coated Cu foam electrode (TCNi-Cu) and a Nafion 324 membrane, the degradation capacity of gaseous toluene was significantly improved.
Article
Chemistry, Organic
Xingwei Cai, Yang Shen, Wei Li, Wentao Zhan, Fanjun Zhang, Chen Xu, Heng Song
Summary: In this study, an efficient tungsten-catalyzed homogeneous system was developed for the selective synthesis of various azoaromatics, azoxyaromatics, and 2-substituted indolone N-oxides from anilines. This was achieved by regulating the reaction solvent with peroxide as a terminal oxidant under additive-free conditions. These findings not only provide an experimental framework for exploring tungsten catalysis in organic synthesis but also offer an efficient and convenient tactic for the selective oxidation of anilines.
Review
Chemistry, Multidisciplinary
Chenxi Duan, Chunming Cui
Summary: Low valent group 14 compounds with diazaborolyl substituents exhibit unique structures and reactivity due to the combination of sigma-electron donation and steric hindrance. The modulation of the HOMO-LUMO gap by the diazaborolyl substituents results in novel reaction patterns in the activation of small molecules and inert chemical bonds.
CHEMICAL SOCIETY REVIEWS
(2024)
Article
Chemistry, Inorganic & Nuclear
Zhiwei Peng, Shu Li, Ao Li, Jiaming Liao, Yiman Wang, Xudong Li, Wei Meng, Jian Zhang
Summary: This article describes the synthesis of an enantiomeric pair of 3d-3d heterometallic clusters in an aqueous solution without heating. The crystal structures reveal a five-layered core structure with a slightly distorted tetradecahedron composed of Mn and Cu ions. Magnetic measurements show that these clusters exhibit slow relaxation of their magnetization vectors.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Organic
Flip Holtrop, Christoph Helling, Martin Lutz, Nicolaas P. van Leest, Bas de Bruin, J. Chris Slootweg
Summary: We present a combined theoretical and experimental investigation on the potential isolation of an encounter complex enabled by enhancement of London dispersion forces between a sterically encumbered Lewis acid and base pair. The study involved the bulky triarylamine N(3,5-tBu(2)C(6)H(3))(3) and the novel triarylborane B(3,5-tBu(2)C(6)H(3))(3), leading to the isolation of a 1:1 co-crystal of both FLP components.
Article
Chemistry, Multidisciplinary
Kai Oberdorf, Patrick Grenzer, Pauline Pfister, Anna Hanft, Anna Rempel, Crispin Lichtenberg
Summary: The reactivity of a literature-known, ring-strained bismuth amide cation towards unsymmetric heterocumulene substrates has been investigated. Reactions with ketenes, isocyanates, and isothiocyanates proceed via facile insertion of the heterocumulene in the Bi-N bond of the cationic bismuth amide. Unexpected differences in the regioselectivity of these insertion reactions have been observed, leading to unprecedented heterocycle motifs. Parameters controlling the regioselectivity have been identified through experimental and theoretical investigations.
Article
Chemistry, Multidisciplinary
Soumyadeep Chakrabortty, Katharina Konieczny, Felix J. de Zwart, Eduard. O. Bobylev, Eszter Barath, Sergey Tin, Bernd H. Mueller, Joost N. H. Reek, Bas de Bruin, Johannes G. de Vries
Summary: Researchers achieved enantioselective hydrogenation of cyclic enamides using an earth-abundant cobalt-bisphosphine catalyst. The catalytic system, CoCl2/(S,S)-Ph-BPE, reduced trisubstituted carbocyclic enamides to saturated amides with high activity and excellent enantioselectivity (up to 99%). The methodology can be extended to the synthesis of chiral amines by base hydrolysis of the hydrogenation products. Preliminary mechanistic investigations suggested a sigma-bond-metathesis pathway for the hydrogenation of the carbon-carbon double bond, involving a high spin cobalt (II) species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Johanna Heine, Benjamin Peerless, Stefanie Dehnen, Crispin Lichtenberg
Summary: Key challenges in modern synthetic chemistry include the design of reliable, selective, and more sustainable synthetic methods, as well as the development of promising candidates for new materials. Molecular bismuth compounds offer valuable opportunities as they show a spectrum of properties that is yet to be fully exploited. Recent findings highlight the essential contributions to the synthesis, analyses, and utilization of ionic bismuth compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Catriona C. James, Petrus C. M. Laan, Bas de Bruin, Joost N. H. Reek
Summary: Olefin metathesis catalysts, such as AquaMet, are susceptible to decomposition under biologically relevant conditions. Current stabilizing strategies have limited applicability under these conditions. Encapsulation of AquaMet within a supramolecular metallocage, with nitrate counterions, enhances the catalyst activity. Replacement of AquaMet's chloride ligands with nitrates through simple anion-exchange leads to higher yields of ring-closed product under aqueous and biological conditions. This kinetic protection strategy of transition metal catalysts may find applications in other in vivo catalytic reactions.
Article
Chemistry, Multidisciplinary
Demi D. Snabilie, Eva J. Meeus, Roel F. J. Epping, Zhiyuan He, Minghui Zhou, Bas de Bruin
Summary: Transition metal radical-type carbene transfer catalysis is a sustainable and atom-efficient method for C-C bond formation. Understanding off-cycle and deactivation pathways can lead to solutions for avoiding catalyst deactivation and reveal novel reactivity for new applications, stimulating further development of radical-type carbene transfer reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
David A. Poole III, Eduard O. Bobylev, Bas de Bruin, Simon Mathew, Joost N. H. Reek
Summary: This article investigates the self-assembly of spherical three-dimensional (3D) cages composed of palladium(II) and pyridyl ligands. The self-assembly process is found to be sensitive to the solvents, reagents, and/or reactants used, which hinders the development of desired palladium-based cages. The study reveals that ligand substitution can be facilitated by endogenous supporting ligands derived from the solvents, reagents, and reactants.
INORGANIC CHEMISTRY
(2023)
Editorial Material
Chemistry, Multidisciplinary
Kai Oberdorf, Patrick Grenzer, Pauline Pfister, Anna Hanft, Anna Rempel, Crispin Lichtenberg
Article
Chemistry, Multidisciplinary
Andreas Stoy, Malte Juergensen, Christina Millidoni, Chantsalmaa Berthold, Jacqueline Ramler, Sebastian Martinez, Magnus R. Buchner, Crispin Lichtenberg
Summary: Dynamic covalent chemistry is a powerful tool in synthetic chemistry, allowing for reversible generation of novel structural motifs. This study demonstrates the application of dynamic covalent chemistry to heavy p-block elements, expanding the range of compounds that can be accessed using this approach.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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
Jasper Biemolt, Eva J. Meeus, Felix J. de Zwart, Jeen de Graaf, Petrus C. M. Laan, Bas de Bruin, Thomas Burdyny, Gadi Rothenberg, Ning Yan
Summary: Immobilizing molecular catalysts on electrodes is crucial for electrochemical applications. The study demonstrates a bottom-up approach for constructing a conjugated C-C bond between the Vulcan carbon electrode and an organometallic catalyst without introducing any foreign elements. The synthesized catalyst exhibits high activity and selectivity for the oxygen reduction reaction compared to the homogeneous counterpart, making it a promising candidate for electrochemical applications.
Article
Chemistry, Multidisciplinary
Subrata Das, Andreas W. Ehlers, Sima Patra, Bas de Bruin, Buddhadeb Chattopadhyay
Summary: A concept for intermolecular C-N cross-coupling amination has been discovered using tetrazoles and aromatic and aliphatic azides with boronic acids under iron-catalyzed conditions. The reaction follows an unprecedented metalloradical activation mechanism, different from traditional metal-catalyzed C-N cross-coupling reactions. The wide scope of this reaction has been demonstrated by employing various tetrazoles, azides, and boronic acids. Moreover, the reaction has shown potential for applications in medicinal chemistry, drug discovery, and pharmaceutical industries, as demonstrated by late-stage aminations and synthesis of a drug candidate.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Kai Oberdorf, Anna Hanft, Xiulan Xie, F. Matthias Bickelhaupt, Jordi Poater, Crispin Lichtenberg
Summary: The uptake and release of small molecules pose significant challenges in synthetic chemistry. By combining small molecule activation with subsequent transformations, new reactivity patterns can be generated, opening up new possibilities for research in this field. In this study, the reaction between CO2 and CS2 with cationic bismuth(iii) amides was investigated. CO2 uptake resulted in isolable but metastable compounds, which underwent CH activation upon CO2 release. These transformations were successfully transferred to the catalytic regime, resembling CO2-catalyzed CH activation. The CS2 insertion products were thermally stable, but under photochemical conditions, they selectively underwent reductive elimination to form benzothiazolethiones. Furthermore, the low-valent inorganic product of this reaction, Bi(i)OTf, was trapped, demonstrating the first example of light-induced bismuthinidene transfer.
Review
Chemistry, Multidisciplinary
Kai Oberdorf, Crispin Lichtenberg
Summary: The creative design and exploration of new bonding motifs and molecular architectures in main group chemistry have expanded the reactivity boundaries in this field. Activation of small molecules serves as a benchmark reaction and offers opportunities for the development of innovative synthetic methods. Recent advances have been made in compounds based on heavy p-block elements, which possess unique properties originating from their high atomic number, setting them apart from more established species in small molecule activation. Challenges and opportunities arising from this scenario are analyzed and highlighted.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Eduard. O. Bobylev, Leonardo Passerini, Felix J. de Zwart, David A. Poole, Simon Mathew, Martina Huber, Bas de Bruin, Joost N. H. Reek
Summary: In this study, a post-assembly modification approach is described to selectively coordinate transition metals in Pd12L24 cuboctahedra. The method involves the preparation of Pd12L24 nanospheres with protonated nitrogen donor ligands that are covalently linked at the interior. Selective formation of different coordination forms of the transition metals is achieved by using different nitrogen donor ligands. Experimental and computational investigations support the presence of complexes at precise locations in the nanospheres.
