Article
Chemistry, Multidisciplinary
Yukihiro Murata, Cihan Ozen, Satoshi Maeda, Takanori Fukushima, Yoshiaki Shoji
Summary: A three-coordinate chloroborane molecule with a borane-olefin proximity effect undergoes a skeletal rearrangement upon chloride abstraction, resulting in the formation of a three-dimensional macrocyclic molecule featuring a borocenium structure.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Libo Xiang, Junyi Wang, Ivo Krummenacher, Krzysztof Radacki, Holger Braunschweig, Zhenyang Lin, Qing Ye
Summary: In this article, we presented the 3D analogues of N-heterocyclic carbene (NHC)-stabilized 9-borafluorenium and 9-borafluorene radical. The radical was thoroughly characterized using cyclic voltammetry, UV-Vis absorption spectroscopy, electron paramagnetic resonance, and single-crystal X-ray diffraction analyses. The boron-centered radical nature of 9-borafluorene radical was confirmed through DFT calculations and EPR analysis.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Kinga Kaniewska-Laskowska, Anna Ordyszewska, Tomasz Wojnowski, Hanna Halenka, Marcin Czapla, Jaroslaw Chojnacki, Rafal Grubba
Summary: In this study, phosphinoborenium cations stabilized by N-heterocyclic carbenes were synthesized and their structures and reactivity were investigated. The results showed that these compounds have specific structures and chemical properties, and can act as both phosphinoborane and phosphido group donors in certain reactions.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Haopeng Gao, Robert Mueller, Elisabeth Irran, Hendrik F. T. Klare, Martin Kaupp, Martin Oestreich
Summary: Potent main-group Lewis acids can activate element-hydrogen bonds. By designing a neutral precursor, the rivalry for hydride between silylium- and borenium-ion centers was investigated, revealing a novel Si-H-B linkage.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Tomasz Sokolnicki, Mashael M. Alharbi, Yara van Ingen, Shahnaz Rahim, Milan Pramanik, Alberto Roldan, Jedrzej Walkowiak, Rebecca L. Melen
Summary: This paper compares the reactivity of a series of triaryl borates B(OArx)(3) as catalysts for the hydroboration of alkenes and alkynes. It was found that commercially available B(OPh)(3) performed the poorest, while catalysts with o-F atoms showed much better performance.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Jack Emerson-King, Adrian B. Chaplin
Summary: The synthesis and solid-state characterization of a heterobimetallic rhodium(III)/silver(I) complex [Rh(2,2'-biphenyl)(CxP(2))Cl]superset of Ag+ is reported, in which CxP(2) is a trans-spanning calix[4]arene-based diphosphine ligand and the silver cation is dative bond to the chloride ligand within the cavity of the macrocycle.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Wei Lu, Nicola Hensiek, Koushik Saha, Rian D. D. Dewhurst, Marcel Haerterich, Conor Pranckevicius, Stephan Hagspiel, Maximilian Dietz, Ivo Krummenacher, Holger Braunschweig
Summary: Stable symmetrical and unsymmetrical dicationic tetraboranes with an electron-precise tetraborane chain were synthesized and characterized. The reactions of these tetraboranes with reductants/bases led to different outcomes depending on the conditions used, including reduction and rearrangement of the tetraborane chain, cleavage of the tetraborane chain, and reduction of the supporting ligands. The zwitterionic alkylidene borate-borenium species formed can be considered as analogues of base-stabilized diborenes, and they exhibit a highly polarized B-B bond.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Yizhou Yang, Yuliang Xu, Huadong Wang
Summary: Non-metal-catalyzed hydrogenation of arenes is a sustainable and environment-friendly approach for the synthesis of cyclohexane derivatives. In this study, a borenium-ion catalyst system was developed to effectively hydrogenate monocyclic arenes. Moreover, the metal-free catalytic system allows for selective partial or full hydrogenation of naphthalene and anthracene by modifying the reaction conditions. Mechanism studies suggest that the H2 splitting mediated by borenium-arene occurs before the rate-limiting step, and hydride transfer between the resulting neutral borane and protonated arene is likely the rate-limiting step in the catalytic process.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Jun Mei, Tianwei He, Juan Bai, Dongchen Qi, Aijun Du, Ting Liao, Godwin A. Ayoko, Yusuke Yamauchi, Litao Sun, Ziqi Sun
Summary: The introduction of nanosized iridium (Ir) modifier and optimized exposed surfaces towards electrolytes leads to an efficient Ir-modified BP electrocatalyst with favorable adsorption energies towards catalytic intermediates, showing outstanding pH-universal water splitting performance surpassing most reported BP-based and commercial noble-metal catalysts.
ADVANCED MATERIALS
(2021)
Article
Chemistry, Multidisciplinary
Rui Guo, Xin Zhang, Tong Li, Qianli Li, David A. Ruiz, Liu Leo Liu, Chen-Ho Tung, Lingbing Kong
Summary: In this study, a cationic iminoborane compound was synthesized and characterized. It was found that the compound exhibited both B-centered Lewis acidity and BN multiple bond reactivities, allowing for the construction of various tri-coordinate boron cations. Additionally, initial reactions involving coordination, addition, and cycloadditions were observed, demonstrating the potential to build numerous organoboron species via several synthetic routes.
Article
Chemistry, Multidisciplinary
Yuzhong Wang, Phuong M. Tran, Mitchell E. Lahm, Yaoming Xie, Pingrong Wei, Earle R. Adams, John N. Glushka, Zichun Ren, Vladimir V. Popik, Henry F. Schaefer, Gregory H. Robinson
Summary: In this study, the mechanism of ammonia activation by a carbene-stabilized dithiolene zwitterion was investigated through experimental and computational methods. The synthesis of 4• and 5 was achieved, and it represents the first metal-free ammonia activation via hydrogen atom transfer.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Hiroshi Suzuki, Tsuyoshi Nishikawa, Hiroshi Makino, Makoto Ouchi
Summary: The effect of protecting groups on the polymerization of vinylboronic-acid derivatives has been studied, and it has been found that anthranilamide-protected vinylboronic acid exhibits high polymerization activity and post-transformation capability.
Article
Chemistry, Multidisciplinary
Lu Meng, Ling Zhang, Yihua Zhu, Hongliang Jiang, Yusuf Valentino Kaneti, Jongbeom Na, Yusuke Yamauchi, Dmitri Golberg, Hao Jiang, Chunzhong Li
Summary: This study demonstrates the possibility of enhancing the electrochemical activity of MOF-derived binary metal center catalysts by controlling the form of Fe species, introducing Fe-SBU can improve electroconductivity and reduce the overpotential of the OER reaction.
Article
Chemistry, Organic
Ramalingam Boobalan, Rong-Jie Chein
Summary: The emergence of second-generation sulfur-stabilized borenium cations by halophilic Lewis acid SnCl4 results in highly active chiral Lewis acids that are effective catalysts for [4 + 2] cycloaddition, exhibiting excellent enantioselectivity for a variety of substrates and demonstrating good catalytic efficiency.
Review
Chemistry, Physical
Xinyue Tan, Huadong Wang
Summary: This review summarizes the recent progress in the catalytic C-H borylation of (hetero)arenes, with a focus on synthetic application and reaction mechanisms.
Article
Chemistry, Organic
Lucas Loir-Mongazon, Carmen Antuna-Horlein, Christophe Deraedt, Yann Cornaton, Jean-Pierre Djukic
Summary: In this study, a combination of theoretical and experimental approaches was used to analyze weak interligand noncovalent interactions in Co(IV) [Cp*Co(phpy)X](+) cobaltacycles. The independent gradient model/intrinsic bond strength index (IGM/IBSI) method was employed to evaluate the dependence of the catalytically desired reductive elimination pathway (RE) on the nature of the X ligand. The results showed that the barrier for activation of the RE pathway is directly correlated with the IBSI of the X-to-carbanionic chelate's carbon, indicating the possibility of in silico prediction of efficient Cp*Co-catalyzed directed X-functionalization of an aromatic C-H bond based on X ligand properties. Experimental evidence supported the theoretical conclusions.
Article
Chemistry, Multidisciplinary
Kai Zhang, Philip A. A. Hope, Melissa E. El Bitar Nehme, Anthony Linden, Bernhard Spingler, Michel Rickhaus
Summary: This study presents the synthesis, characterization, and properties of a heterocyclic compound containing three fused heptagon rings. The unique strained structure and self-assembly properties of the compound result in red-shifted absorption and concentration-dependent emission profiles. Additionally, the compound exhibits a lower oxidation potential compared to its non-bridged analog. This research opens up new avenues for understanding the structure-property relationships of curved pi-aromatics and constructing increasingly complex pi-frameworks.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Carmen Antuna-Horlein, Fule Wu, Christophe Deraedt, Corinne Bouillet, Jean-Pierre Djukic
Summary: The reactivity of a 2-phenylpyridine-derived metallacycle towards Et3SiH and hydrides was studied. Treatment of the same Co(III) complex with Na[BHEt3] resulted in its decomposition into cobalt nanoparticles. The decomposition of the metallacycle involves the formation of a hydrido-cobalt(III) intermediate, which was detected by H-1 NMR spectroscopy. The Co nanoparticles produced from the metallacycle and Na[BHEt3] serve as catalysts for the hydrosilylation of arylketones into silylalkyl ethers.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Engineering, Electrical & Electronic
Guilherme Baumgarten, Morgan Madec, Duc-Vinh Nguyen, Lucas Werling, Joris Pascal, Chunchesh Malangi Gajendramurthy, Philippe Bertani, Jean-Pierre Djukic, Luc Hebrard
Summary: Miniaturized nuclear magnetic resonance (NMR) devices are becoming popular due to their flexible use in various applications. However, the lack of a sufficiently homogeneous static magnetic field $B_{0}$ has hindered the development of miniaturized NMR systems. This article proposes an efficient simulator that can evaluate the quality of the static magnetic field and its impact on NMR spectrum resolution. The simulator has been validated and applied to a real spectrum, showing its applicability and potential for improvement.
IEEE TRANSACTIONS ON MAGNETICS
(2023)
Article
Chemistry, Physical
Assia Mili, Souheyla Chetioui, Amel Djedouani, Jean-Pierre Djukic, Abeer AlObaid, Abdelkader Zarrouk, Ismail Warad
Summary: A novel isomer ligand has been synthesized successfully, and the tautomerization mechanism from diazene to hydrazine has been confirmed by computational and experimental methods. The kinetic isomer of hydrazine form has been identified as the preferred form based on XRD measurements.
JOURNAL OF MOLECULAR STRUCTURE
(2023)
Article
Chemistry, Multidisciplinary
Masoumeh Behzadi, Chunchesh Malangi Gajendramurthy, Melanie Boucher, Christophe Deraedt, Yann Cornaton, Lydia Karmazin, Nathalie Gruber, Philippe Bertani, Jean-Pierre Djukic
Summary: The performance of six newly synthesized benzo[h]quinoline-derived acetonitrilo pentamethylcyclopentadienyl iridium(III) tetrakis(3,5-bis-trifluoromethylphenyl)borate salts with different substituents was evaluated in two reactions involving the electrophilic activation of the Si-H bond. The catalytic efficiency was found to be directly dependent on the electronic effect of the substituents, as confirmed by theoretical assessment. The analysis of the Ir-Si-H interactions revealed that the Ir-H bond is the most cohesive bond in the hydridoiridium(III)-silylium adducts, while the Ir-Si bond is a weak donor-acceptor bond.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Editorial Material
Chemistry, Multidisciplinary
Kai Zhang, Philip A. Hope, Melissa El Bitar Nehme, Anthony Linden, Bernhard Spingler, Michel Rickhaus
Summary: The cover of this issue features the research conducted by Michel Rickhaus and his team at the University of Zurich. The image showcases the discovery of the highly contorted azatriseptane molecule, which comprises three fused seven-membered rings surrounding a central nitrogen atom. Read the full article at 10.1002/chem.202203954.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Manuel Luca Besmer, Henrik Braband, Thomas Fox, Bernhard Spingler, Alfred P. Sattelberger, Roger Alberto
Summary: This study investigates the role of metal-ligand cooperativity in the activation of various bonds using a radioactivetransition metal Tc-99 compound. The compound showed reactivity with CO2 and H-2, resulting in the formation of new complexes. Different ligands were isolated through reactions and their spectroscopic analyses were performed. The study demonstrates the application of metal-ligand cooperativity on substrates with weakly acidic protons.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Lukas Schneider, Martina Kalt, Samuel Koch, Shanmugi Sithamparanathan, Veronika Villiger, Johann Mattiat, Flavia Kradolfer, Ekaterina Slyshkina, Sandra Luber, Mathias Bonmarin, Caroline Maake, Bernhard Spingler
Summary: This article reports six novel and easily accessible BODIPY-based agents for cancer treatment that exhibit both photodynamic and photothermal activities, and do not rely on the generation of reactive oxygen species for cytotoxicity. These agents demonstrate high photocytotoxicity and low dark toxicity in different cancer cell lines. Under hypoxic conditions, they exhibit oxygen-independent photothermal mechanisms, making them potential candidates for overcoming limitations in current cancer therapy.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Medicine, Research & Experimental
Lea P. Gergely, Cigdem Yuceel, Umit Isci, Florentin S. Spadin, Lukas Schneider, Bernhard Spingler, Martin Frenz, Fabienne Dumoulin, Martina Vermathen
Summary: In this study, PVP and F127 micelles were found to have high encapsulation abilities for water-soluble zinc phthalocyanine molecules and efficiently catalyze singlet oxygen formation. This result suggests that polymeric micelles can serve as effective delivery systems to optimize the performance of phthalocyanine molecules as photosensitizers.
MOLECULAR PHARMACEUTICS
(2023)
Article
Crystallography
Bernhard Spingler
Summary: The crystal structure of a biologically active compound reveals a network of hydrogen bonding interactions.
ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Chuhao Lin, Yujie Jin, Jizeng Sun, Zehua Ye, Tao Chen, Jiyong Liu, Simon Duttwyler
Summary: Penta-iodination of the B2-6 positions of the CB11 monocarborane cluster was achieved for the first time. The product structures were fully characterized and confirmed by X-ray crystal structures. The synthetic method relied on palladium catalysis/B-H activation, assisted by the C1-COOH directing group. This one-pot procedure enables penta-iodination and subsequent decarboxylation under convenient conditions, showing complementary regioselectivity compared to commonly observed reactivity of CB11 clusters.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Loic Groslambert, Yann Cornaton, Matej Ditte, Emmanuel Aubert, Patrick Pale, Alexandre Tkatchenko, Jean-Pierre Djukic, Victor Mamane
Summary: Telluronium salts [Ar2MeTe]X were synthesized and their Lewis acidic properties in solution were investigated using physical and theoretical methods. The study revealed the electrophilicity of the Te centers and the ability of telluroniums to form Lewis pairs. The affinity of telluroniums for OPPh3 was determined by state-of-the-art computational methods, showing the importance of Coulombic and dispersion interactions in solution.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)