Article
Chemistry, Multidisciplinary
Yuta Nishimura, Takashi Harimoto, Takanori Suzuki, Yusuke Ishigaki
Summary: A nitrogen-centered heptalene, azaheptalene, was designed as a representative of a new class of redox-responsive molecules with a large steric strain. The pentabenzo derivative of azaheptalene was efficiently synthesized by a palladium-catalyzed one-pot reaction. Bromination led to mono- and dibrominated derivatives, with the latter exhibiting near-infrared absorption as isolable radical cation species. Optically pure azaheptalenes with P- or M-helicity showed strong chiroptical properties, which could be changed by an electric potential.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Manfei Zhou, Lijun Mao, Yan-Fei Niu, Xiao-Li Zhao, Xueliang Shi, Hai-Bo Yang
Summary: This study investigates the redox behavior and radical cation species of triphenylamines with various substituents. The results demonstrate that resonance hybrid and steric protection contribute to the stability of triphenylamine radical cations. Additionally, further oxidation leads to unexpected demethylation. These findings provide new insights into the unique redox properties of triphenylamines substituted with 4-anisyl groups.
CHINESE CHEMICAL LETTERS
(2022)
Article
Multidisciplinary Sciences
Clorice R. Reinhardt, Daniel Konstantinovsky, Alexander Soudackov, Sharon Hammes-Schiffer
Summary: This article presents a kinetic model that describes the reversible radical transfer in the enzyme ribonucleotide reductase (RNR). The model is based on experimental studies and provides insights into the time evolution and factors influencing radical transport in RNR.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Chemistry, Inorganic & Nuclear
Kazuishi Fukuda, Takuma Harada, Nobuharu Iwasawa, Jun Takaya
Summary: In this study, bis(o-phosphinophenyl)zinc derivatives were synthesized, and it was found that the presence of specific substituents significantly accelerated the transmetallation reaction between metals, resulting in the selective formation of diarylzinc.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Yilin Chen, Zhikang Chen, Liuyin Jiang, Jiancheng Li, Yiling Zhao, Hongping Zhu, Herbert W. Roesky
Summary: Various electron-transferable oxidants were employed to react with specific organic compounds, resulting in the formation of stable radical cations, dications, and paired anions. The newly obtained compounds were characterized using UV-vis absorption spectroscopy, X-ray crystallography, EPR, and NMR techniques.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Avijit Maiti, Benedict J. Elvers, Sachinath Bera, Felix Lindl, Ivo Krummenacher, Prasanta Ghosh, Holger Braunschweig, Cem B. Yildiz, Carola Schulzke, Anukul Jana
Summary: In this study, cyclic(alkyl)(amino)carbenes (CAACs) were found to be one-electron reductants, forming transient radical cations as detected by EPR spectroscopy. The reactivity of the disclosed CAACs was utilized to synthesize a new class of Thiele and Chichibabin hydrocarbons based on acyclic(amino)(aryl)carbene. Additionally, the acyclic(amino)(aryl)carbene-based Chichibabin's hydrocarbon showed a significant population of the triplet state at room temperature.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Yilin Chen, Zhikang Chen, Liuyin Jiang, Jiancheng Li, Yiling Zhao, Hongping Zhu, Herbert W. Roesky
Summary: This study utilized various electron-transferable oxidants to react with compounds, forming a series of stable radical cations and dication species, and synthesized compounds with different structural features, which were characterized by various spectroscopic techniques.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Yupeng Guo, Xingye Wu, Bingxia Hou, Qin Xiang, Yong Ni, Jinling Li, Zhe Sun
Summary: A highly persistent benzoanthracenyl radical (BAR1) protected by five substituents at strategic positions is synthesized. BAR1 exhibited a half-life time of 108 h in air-saturated solution, allowing for detailed characterization. The combined experimental and theoretical study reveals the properties associated with its asymmetric structure and spin distribution.
CHEMICAL RESEARCH IN CHINESE UNIVERSITIES
(2023)
Article
Chemistry, Multidisciplinary
Ke Chai, Jicheng Zhang, Qingyuan Li, Deniz Wong, Lirong Zheng, Christian Schulz, Maciej Bartkowiak, Dmitry Smirnov, Xiangfeng Liu
Summary: This study proposes a comprehensive structural modulation of Li-rich cathodes by introducing oxygen vacancies and P doping to mitigate critical issues such as oxygen escape, cation migration, and voltage decay. The modulated cathode exhibits improved performance, including high-rate capability, cycling stability, restrained voltage decay, and elevated working voltage.
Article
Chemistry, Multidisciplinary
Yanbo Mei, Xiaodan Chen, Rui Wei, Xiao-Yong Chang, Lizhi Tao, Liu Leo Liu
Summary: This study reports the synthesis, isolation, and characterization of a radical anion with Si and P. The species features a perfectly planar Si2P2 four-membered ring, making it the first Si- and P-containing analog of a bicyclo[1.1.0]butane radical anion. The bonding motif of this unusual species was investigated using experimental and computational methods, revealing the presence of a 2-center-3-electron pi bond between the bridgehead P atoms.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Polymer Science
Zixin An, Shilong Zhu, Zesheng An
Summary: Photocatalytic reversible deactivation radical polymerization (RDRP) allows spatial-temporal regulation of radical polymerization using sustainable solar light, with heterogeneous photocatalysts offering additional advantages such as facile preparation, tunable photoelectronic properties, and potential for catalyst recyclization.
Article
Chemistry, Multidisciplinary
Pengju Li, Alexander M. Deetz, Jiaming Hu, Gerald J. Meyer, Ke Hu
Summary: This study presents two photocatalytic pathways for chloride oxidation, which generate different oxidation products through different excitation modes. By these pathways, chlorination of unactivated C(sp(3))-H bonds in organic compounds can be achieved.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Jinghua Huang, Shuzhi Hu, Xianzhi Yuan, Zhipeng Xiang, Mingbao Huang, Kai Wan, Jinhua Piao, Zhiyong Fu, Zhenxing Liang
Summary: A novel organic molecule has been developed as a reversible six-electron storage electrolyte for ARFB, evolving from a radical to a biradical and then to a quinoid structure. With high diffusion coefficient and rate constant, the flow battery achieves high specific capacity and peak power density in a demonstration unit.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Polymer Science
Francois Magnan, Jasveer S. Dhindsa, Michael Anghel, Paul Bazylewski, Giovanni Fanchini, Joe B. Gilroy
Summary: Stable radical polymers have been widely studied for their applications in various fields, but the range of synthetic strategies is currently limited. Common methods include transition-metal catalyzed polymerization and sequential polymerization of monomers containing radical precursors, which are then converted to radicals post-polymerization. Copper-assisted azide-alkyne cycloaddition chemistry has been used sparingly, mainly for producing pi-conjugated and particle-bound polymers.
Review
Chemistry, Multidisciplinary
Ali Bagheri, Christopher M. Fellows, Cyrille Boyer
Summary: 3D printing technology has revolutionized the fabrication of advanced materials, but the challenge remains in printing polymer materials with post-printing transformability. Traditional radical polymerization used in photopolymerization-based 3D printing offers limited control over chain growth and architecture, unlike the reversible deactivation radical polymerization which allows for network homogeneity tuning and the production of reactivatable species for subsequent processes. RDRP-based networks have advantages over conventionally formed networks in terms of controllability and post-synthetic transformations.
Editorial Material
Chemistry, Inorganic & Nuclear
Shigeyoshi Inoue, Rebecca L. Melen, Sjoerd Harder
Summary: The development in the field of main group catalysis has led to a better understanding of main group compounds and rational design of their reactivity. Ongoing research has led to the discovery of new classes of more environmentally friendly, cheap, and abundant main group catalysts as alternatives to transition metal catalysts.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Andreas Saurwein, Matthias Nobis, Shigeyoshi Inoue, Bernhard Rieger
Summary: This study reports a novel silylene with a phosphinimide ligand, which exhibits silylene-like behavior through activation reactions and can undergo olefin exchange. This research contributes to the application of phosphinimide ligands in low-valent silicon chemistry.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Sebastian Stigler, Mihyun Park, Amelie Porzelt, Arseni Kostenko, Daniel Henschel, Shigeyoshi Inoue
Summary: The synthesis and characterization of a compound [mTer(IMe4)2Si -> BH3][OTf] and its highly unusual hydride dication [mTer(IMe4)2SiH][OTf]2 are reported. The reaction outcome is strongly influenced by the borane source, and the unprecedented nucleophilic character of the compound [mTerSi(IMe4)2][OTf] is elucidated by density functional theory calculations.
Article
Chemistry, Multidisciplinary
Xuan-Xuan Zhao, Shiori Fujimori, John A. Kelly, Shigeyoshi Inoue
Summary: A novel stannylenoid compound was synthesized by reacting lithium aryl(silyl)amide with SnCl2, and further transformations of the stannylenoid compound were achieved. All compounds were characterized by NMR, elemental analysis, and X-ray structural determination.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Huihui Xu, Arseni Kostenko, Catherine Weetman, Shiori Fujimori, Shigeyoshi Inoue
Summary: Facile access to dimeric heavier aluminum chalcogenides [(NHC)Al(Tipp)-mu-Ch](2) (NHC=IiPr, IMe4; Tipp=2,4,6-iPr(3)C(6)H(2); Ch=Se, Te) by treatment of NHC-stabilized aluminum dihydrides with elemental Se and Te is reported. The higher affinity of IMe4 in comparison with IiPr toward the Al center in [(NHC)Al(Tipp)-mu-Ch](2) can be used for ligand exchange. Additionally, the presence of excess IMe4 allows for cleavage of the dimers to form a rare example of a neutral multiply bonded heavier aluminum chalcogenide in the form of a tetracoordinate aluminum complex, (IMe4)(2)(Tipp)Al=Te. This species reacts with three equivalents of CO2 across two Al-C-NHC and the Al=Te bond affording a pentacoordinate aluminum complex containing a dianionic tellurocarbonate ligand [CO2Te](2-), which is the first example of tellurium analogue of a carbonate [CO3](2-).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Huaiyuan Zhu, Arseni Kostenko, Daniel Franz, Franziska Hanusch, Shigeyoshi Inoue
Summary: A novel nontransient acyclic iminosilylene compound with a bulky super silyl group and a methylated backbone was isolated. This compound shows intermolecular Bu''chner-ring-expansion-type reactivity, forming silicon analogs of cycloheptatrienes. The reactions with N-heteroarenes are faster and irreversible, resulting in azasilepins with nearly planar seven-membered rings.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Florian S. S. Tschernuth, Lukas Bichlmaier, Shigeyoshi Inoue
Summary: The exceptional catalytic activity of a neutral Si(IV) Lewis superacid was demonstrated in the degradation of oligo- and polyethers via ring closing metathesis. The catalyst showed significantly higher reactivity than comparable Lewis acid catalysts reported in the literature. The high activity was attributed to the bulky perfluorinated substituents blocking a coordination site responsible for catalyst deactivation. However, the catalyst exhibited gradual activity loss when multiple internal product units were present due to mechanistic disparities favoring side-reactions. The cleavage of etheric C-O bonds was ultimately demonstrated by the reaction with diethylether, forming a fully characterized pentavalent silicate species.
Article
Chemistry, Multidisciplinary
Huaiyuan Zhu, Franziska Hanusch, Shigeyoshi Inoue
Summary: The reactivity of acyclic imino(silyl)silylene with N-heterocyclic imine ligand towards small molecules was studied. The silylene showed facile activation of gaseous molecules and could undergo cycloaddition reactions with carbonyl compounds to form oxasilacycles. Reactions with silane, borane, and heavier chalcogens led to the formation of E-H insertion products and neutral three-coordinate silicon-heavier chalcogen double bond complexes.
ISRAEL JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Florian S. Tschernuth, Lukas Bichlmaier, Sebastian Stigler, Shigeyoshi Inoue
Summary: The emerging field of Lewis acidic silanes demonstrates the versability of molecular silicon compounds for catalytic applications. Nevertheless, silicon derivatives still lack in terms of reactivity when compared to boron Lewis acid B(C6F5)3. This study successfully installed perfluorotolyl and perfluorocresolato groups on neutral Si(IV) atoms, and synthesized tetra- and trisubstituted silanes with different acidity levels.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Moritz Ludwig, Daniel Franz, Arturo Espinosa Ferao, Michael Bolte, Franziska Hanusch, Shigeyoshi Inoue
Summary: We report the isolation of three alumanyl silanide anions featuring an Al-Si core stabilized by bulky substituents and a Si-Na interaction. The Al-Si interaction possesses partial double bond character. Reactivity studies suggest a predominant nucleophilic character of the sodium-coordinated silicon center in the Al-Si core, as shown by silanide-like reactivity towards halosilane electrophiles and CH-insertion of phenylacetylene. We also report an alumanyl silanide with a sequestered sodium cation, where cleavage of the Si-Na bond increases the double bond character of the Al-Si core.
Article
Chemistry, Multidisciplinary
Teresa Eisner, Arseni Kostenko, Fiona J. Kiefer, Shigeyoshi Inoue
Summary: The synthesis, characterization, and structures of neutral group 14 diazoolefin complexes and their subsequent transformation into a new cyclic bis-vinyl germylene have been reported.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Mihyun Park, Claudia Schmidt, Sebastian Tuerck, Franziska Hanusch, Simone V. Hirmer, Ingo Ott, Angela Casini, Shigeyoshi Inoue
Summary: A dinuclear gold(I) complex with a strongly donating bis-N-heterocyclic imine ligand was synthesized and characterized. It showed highly selective anticancer effects against non-small cell lung cancer cells, particularly A549 cells. The anticancer effects were not correlated with the amount of gold uptake by the cells but correlated with its selective inhibition of cancer cells overexpressing a specific enzyme.
Article
Chemistry, Multidisciplinary
Arseni Kostenko, Shigeyoshi Inoue
Summary: This study demonstrates the significance of designing the local chemical environment to achieve desired stabilization and reactivity in low-valent main-group centers using iminate ligands.
Article
Chemistry, Multidisciplinary
Lisa Groll, John A. Kelly, Shigeyoshi Inoue
Summary: A new heteroleptic amino(imino)stannylene compound and two homoleptic NHI-stabilized tetrylenes were presented and their structures and reactivities were investigated.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Florian S. Tschernuth, Arseni Kostenko, Sebastian Stigler, Anna Gradenegger, Shigeyoshi Inoue
Summary: The Germanium-centred Lewis superacid Ge(pinF)2 (1) was isolated and characterized by various methods. It was found to exhibit both hard and soft Lewis superacidic properties. The compound can activate silanes and catalyze hydrosilylation reactions. The inverse temperature dependence of the catalytic reaction is attributed to the formation of Germylene Ge(pinF) (3).
DALTON TRANSACTIONS
(2023)
