Review
Chemistry, Inorganic & Nuclear
Yidan Wang, Bo Zhang, Shuai Guo
Summary: The combination of NHC and pincer framework in transition metal complexes has been widely studied and applied in various fields, including catalysis and optical material chemistry. This minireview focuses on the synthesis, reactivity study and applications of metal pincer NHCs.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Kunlong Li, Minghao Huang, Jiliang Zhou
Summary: An unprecedented anionic pincer ligand with pendant phosphazene arms has been synthesized, which can stabilize main-group and transition metal complexes. The phosphazene arms strongly coordinate to the metal centers, while the central amide group alternatively donates one or two pairs of electrons to bind with different metal centers.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Marta Fernandez-Buenestado, Rosie J. Somerville, Joaquin Lopez-Serrano, Jesus Campos
Summary: We present a novel iridium system with a long-tethered PGeP ligand, which allows access to the less common germylene form, never reported before for an 'NHC-type' Ge ligand. Computational studies confirm its bonding, and we demonstrate its application in the catalytic dehydrogenation of formic acid, showcasing the potential of this underdeveloped ligand type.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Amy L. Speelman, Kazimer L. Skubi, Brandon Q. Mercado, Patrick L. Holland
Summary: Recent experimental evidence indicates that during N-2 reduction, the FeMoco of nitrogenase undergoes structural rearrangement, leading to the generation of coordinatively unsaturated iron sites. New designed ligands have shown the potential flexibility in structural arrangement of metal complexes, mimicking the resting state of nitrogenase.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jueri Sekiguchi, Yugo Kazama, Akihiko Ishii, Norio Nakata
Summary: We investigated the reactions of an iminophosphonamido-silylene with different palladium complexes. The reaction with [Pd(PPh3)(4)] yielded a homoleptic tris(silylene)-palladium(0) complex. Surprisingly, the reaction with [PdMe2(tmeda)] resulted in the formation of a novel non-planar mu(3)-silylyne-bridged tetranuclear palladium cluster with palladium atoms in different oxidation states.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Mohd Nazish, Han Bai, Christina M. Legendre, Regine Herbst-Irmer, Lili Zhao, Dietmar Stalke, Herbert W. Roesky
Summary: This work presents the different coordination nature of the bidentate ligand towards gold and silver complexes. Compound 2 exhibits intramolecular aurophilic interaction, while in compound 4, only two P(III) coordinate to Ag(I) with simultaneous oxidative addition of Fluorine.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Hayato Sasaki, Yuki Yokouchi, Takumi Nukazawa, Takeaki Iwamoto
Summary: In this research, a rapid and mild reaction was reported for the synthesis of NHC-coordinated bis(trimethylsilyl)silylene 2, which exhibited coordination to BPh3, addition reactions with 2,3-dimethylbutadiene and Me3SiI, and an unprecedented substitution reaction with (Me3Si)3SiI, generating (Me3Si)3Si-substituted IMe4-coordinated silylene 6.
Article
Chemistry, Multidisciplinary
Jian Xu, Chenshu Dai, Shenglai Yao, Jun Zhu, Matthias Driess
Summary: The paper reports the synthesis of a monoatomic zero-valent tin complex stabilized by a bis(silylene)xanthene ligand and its bis-tetracarbonyliron complex. Density functional theory calculations confirm the genuine stannylone character of the synthesized compound.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Yinhuan Li, Guorong Zhen, Lu Huang, Rong Zhang, Liliang Wang, Fan Qi, Mitsuo Kira, Zhifang Li
Summary: In this study, the synthesis, structural characterization, and density functional theory (DFT) calculations of trinuclear anionic gold clusters ligated by dialkylsilylene and dialkylgermylene were reported.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Weiqin Xu, Leon Maser, Lukas Alig, Robert Langer
Summary: The coordination of a pincer ligand with a protonated carbodiphosphorane as central donor group in the rhodium(I) complex and the different reactivity of rhodium(I) and iridium(I) precursors were studied, leading to the successful synthesis of a CDP-based pincer-type complex.
Article
Chemistry, Physical
Yumiao Ma, Aqeel A. Hussein
Summary: We present a strategy to tune the catalytic behavior of the pincer-Co catalyst by investigating the effect of partners such as (18-crown-6)K+, W(CO)(3), and W(PMe3)(3) on the nitrile hydroboration reaction. The partner's influence on the cobalt center's electron-richness and the donor ability of the pincer ligand is revealed through pi-coordination. These findings suggest a notable partner effect that can be explored by experimentalists to tune the reactivity of catalysts without ligand modification.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Inorganic & Nuclear
Jiawen Lee, Jun Fan, An-Ping Koh, Wan-Jun Joslyn Cheang, Ming-Chung Yang, Ming-Der Su, Cheuk-Wai So
Summary: This study describes the use of an amidinato isopropylmethylamidosilylene catalyst for the efficient hydroboration of carbonyl compounds, resulting in the formation of borate esters. Mechanistic studies reveal the involvement of the Si lone pair electrons and the B vacant p orbital in the reaction process.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Stephen Sproules
Summary: Spectroscopic and computational examination reveals a Class III mixed-valent ground state for the neutral tris-dioxolene complex [V(dbcat)(3)]. The radical is stabilized by delocalization across the ligands mediated by the V(v) center's energy matched d orbital manifold. This electronic structure differs from the tris-dithiolene and tris-diimine analogues with V(iv) and V(ii) ions, respectively.
DALTON TRANSACTIONS
(2022)
Review
Biochemistry & Molecular Biology
Zufar N. Gafurov, Artyom O. Kantyukov, Alexey A. Kagilev, Alina A. Kagileva, Il'yas F. Sakhapov, Ilya K. Mikhailov, Dmitry G. Yakhvarov
Summary: Pincer complexes are important in organometallic chemistry, especially as homogeneous catalysts for organic transformations. Non-symmetrical phosphorus-based pincer nickel complexes have shown higher catalytic activity and have gained increasing attention in recent years. This mini-review focuses on the recent advances in the chemistry of these complexes, including ligand design, synthesis, and catalytic applications.
Article
Chemistry, Multidisciplinary
Ming Li, Sandeep K. Gupta, Sebastian Dechert, Serhiy Demeshko, Franc Meyer
Summary: Synthetic routes have been developed for a dicobalt(I) complex using a unique pyrazolate-bridged dinucleating ligand, showing efficient catalytic activity in the reductive silylation of nitrogen. Protonation leads to the formation of a tetracobalt(I) complex, demonstrating potential in the field of molecular nitrogen fixation catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
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
Teresa Eisner, Arseni Kostenko, Franziska Hanusch, Shigeyoshi Inoue
Summary: An easily isolable silacycloheptatriene was synthesized and the relative concentration of its isomers was controlled by temperature variation. The reactivity of the compound was demonstrated on small molecules.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Ramona Baierl, Arseni Kostenko, Franziska Hanusch, Alexander D. Beck, Shigeyoshi Inoue
Summary: Here, we report the synthesis and isolation of Si(IV) dicationic complexes stabilized by a bidentate N-heterocyclic carbene-phosphinidene (NHCP). These dications exhibit high Lewis acidity and feature a tetracoordinated silicon centre. In addition, dication [2 a] is able to react with diphenylketene by insertion into the Si-P bond.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
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)
Article
Chemistry, Inorganic & Nuclear
Yuzhu Li, Jing Xi, Jesus Ferrando-Soria, Yi-Quan Zhang, Wenyuan Wang, You Song, Yan Guo, Emilio Pardo, Xiangyu Liu
Summary: This study focuses on the synthesis and characterization of two iron(II) complexes, and discovers the significant influence of magnetic anisotropy on field-induced single-ion magnet behavior. Notably, butterfly hysteresis loops were observed in the complexes.
DALTON TRANSACTIONS
(2022)
