Article
Chemistry, Multidisciplinary
Malte Fischer, Samuel Nees, Thomas Kupfer, James T. Goettel, Holger Braunschweig, Christian Hering-Junghans
Summary: Combining (AlCp*)(4), a source of monomeric :AlCp* at elevated temperatures, with (Dip)TerPriPMe(3) (Pn = P, As) cleanly produces pnictaalumenes (Dip)TerPnAlCp* with polarized Pn-Al double bonds and intramolecular stabilization through interactions of Al with a flanking aryl group of the terphenyl substituent on Pn at 80 degrees C. On the other hand, using (Mes)TerPPMe(3) in reaction with 2 equiv of :AlCp* or :AlCp* results in the formation of three-membered 2 pi-aromatic ring systems (Mes)TerP(AlCpx)(2) (x = 3t, *).
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Inorganic & Nuclear
Jinjing Pan, Li Zhang, Yuhao He, Qian Yu, Gengwen Tan
Summary: Magnesium(I) complexes are widely studied as reducing agents in small-molecule activation and organometallic synthesis. Despite successfully isolating a magnesium(I) species in this study, no stable mononuclear magnesium(I) compounds have been identified, with the complex identified as essentially a magnesium(II)-radical dianion complex based on spectroscopic studies and theoretical calculations.
Review
Chemistry, Inorganic & Nuclear
Liliang Wang, Yinhuan Li, Zhifang Li, Mitsuo Kira
Summary: In the past three decades, a significant number of isolable silylenes have been synthesized and studied for their unique properties and characteristic reactions. This review focuses on the differences in properties and reactivities among stable silylenes and includes discussion of some extra-coordinated silylenes. The review covers substituent effects on Si-29 NMR chemical shift, UV-vis absorption maxima, MO properties, as well as diverse reactions and mechanisms of silylenes.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Jian Liu, Melissa M. Bollmeyer, Yujeong Kim, Dengmengfei Xiao, Samantha N. MacMillan, Qi Chen, Xuebing Leng, Sun Hee Kim, Lili Zhao, Kyle M. Lancaster, Liang Deng
Summary: Mononuclear Pd(I) species are potential intermediates in Pd-catalyzed reactions, and a Pd(I) amido complex has been isolated and characterized in this study, revealing its electronic features and reactivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Andre Schumann, Jonas Bresien, Malte Fischer, Christian Hering-Junghans
Summary: A scalable synthetic protocol for cyclotriarsanes has been described in this study, allowing for the investigation of their reactivity towards different ligands. This method provides direct access to a variety of NHC-arsinidene adducts.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Hong Liu, Kai Li, Shengli Huang, Hailong Yan
Summary: This study reports the first isolation and comprehensive characterization of vinylidene orlho-quinone methides (VQMs), demonstrating their significant role in asymmetric catalysis and potential as starting materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Norihiko Takeda, Riku Suganuma, Motohiro Yasui, Masafumi Ueda
Summary: An efficient approach to access isolable beta-chloroenamines via nucleophilic addition/dehydration of alpha-chloro N-alkoxylactam with organolithium and Grignard reagents is reported. This approach is amenable to the synthesis of beta-chloroenamines with various C(sp) and C(sp(2)) units, such as alkyne, aryl, and heteroaryl moieties. The sequential reaction has a broad substrate scope and can be carried out for a scalable synthesis of beta-chloroenamines. Control experiments suggested that both chloro and alkoxy groups act as inductive electron-withdrawing substituents to improve the stability of the enamines.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
McKenna K. Goetz, Joseph E. Schneider, Alexander S. Filatov, Kate A. Jesse, John S. Anderson
Summary: This study reports the isolation and characterization of a new terminal Co-III-oxo complex capable of hydroxylation of aliphatic C-H bonds. The experimental and DFT analysis reveal that the reaction is endergonic at the initial C-H activation step but driven by an extremely exergonic radical rebound step, similar to cytochrome P450 enzymes. The rapid C-H hydroxylation reactivity displayed in this well-defined system provides insight into biological systems and synthetic oxidants.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Shunya Hara, Shigekazu Ito
Summary: The catalytic intermolecular [2+2] cycloaddition of electron-rich alkynes and trifluoroiminopyruvate was demonstrated, affording the corresponding CF3-substituted isolable 2-azetines. Using titanium(IV) tetrachloride as a catalyst effectively promoted the desired [2+2] cycloaddition, providing 2-azetines. The regioselectivity was complete with electron-rich aryl-substituted inner alkynes, and a silyl group was effective for inducing the dominant [2+2] cycloaddition pathway, leading to the formation of a 6-membered cyclic sulfonamide.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Maria L. G. Sansores-Paredes, Storm van der Voort, Martin Lutz, Marc-Etienne Moret
Summary: Nickelacyclobutanes are reactive intermediates in the reaction of nickel carbenes and olefins, which can selectively decompose into cyclopropanes, metathesis, or beta-hydride elimination pathways depending on the coordination of different coligands. DFT calculations provide insight into the mechanisms of these pathways.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
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, Organic
Pavel K. Elkin, Nathaniel D. Durfee, Viresh H. Rawal
Summary: The study explores the cycloaddition reactions of 1-alkoxy-1-amino-1,3-butadienes, which are prepared from crotonic acid chloride and its derivatives. These doubly activated dienes react with electron-deficient dienophiles to form cycloadducts under mild conditions, providing versatile building blocks for complex molecule synthesis. Hydrolysis of the DA cycloadducts yields 6-substituted and 6,6-disubstituted 2-cylohexenones, while the corresponding HDA cycloadducts afford 6-substituted 5,6-dihydropyran-2-ones.
Article
Chemistry, Multidisciplinary
Ming Chen, Zhaoyin Zhang, Zihao Qiao, Lili Zhao, Zhenbo Mo
Summary: We have successfully synthesized a stable plumbylone (3) by reducing a bromodigermylplumbylene (2) with 2.2 equiv of potassium graphite (KC8). The single-crystal X-ray diffraction study revealed the molecular structure of 3, featuring a two-coordinated Pb center with an acute Ge-Pb-Ge bond angle. Computational studies indicated that complex 3 possesses a singlet electronic ground state with a Pb-0 center. Its high thermal stability can be attributed to the delocalization of pi electrons over the Ge-Pb-Ge moiety. Additionally, complex 3 has shown promising synthetic utility in delivering Pb-0 atoms to organic azides and performing metathesis reactions with GeCl2 center dot dioxane to produce bis(germylene)-stabilized germylone (5).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Aishabibi Kassymbek, Dmitry G. Gusev, Anton Dmitrienko, Melanie Pilkington, Georgii Nikonov
Summary: This study explores the reactions of NacNacGa with various compounds, resulting in the formation of nitrilimine compounds, metallated diazo species and isonitrile compounds; DFT calculations reveal the reaction mechanisms involving intermediate alkylidene compounds and boryl migration.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Corey A. Richards, Nigam P. Rath, Jamie M. Neely
Summary: Transition metal imide-mediated C-N bond formation is a powerful strategy for introducing nitrogen into organic compounds. Stoichiometric experiments revealed a catalyst deactivation pathway, which was suppressed in the presence of a coordinating additive. These insights were instrumental in identifying reaction conditions that allow for turnover of the iron catalyst.
Article
Chemistry, Multidisciplinary
Xuan-Xuan Zhao, Tibor Szilvasi, Franziska Hanusch, John A. Kelly, Shiori Fujimori, Shigeyoshi Inoue
Summary: The germanium iron carbonyl complex and the tin iron carbonyl complex were prepared and showed reversible formation of bis(tetrylene) and tetrylene-tetrylone character. Computational analysis further explained the reduction pathway from the chlorotetrylenes to the corresponding complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
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, 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)
