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)
Article
Chemistry, Multidisciplinary
Dawei Li, Lichao Ning, Qiliang Luo, Shiyu Wang, Xiaoming Feng, Shunxi Dong
Summary: An array of rare-earth bis(aminobenzyl) complexes supported by imidazolin-2-iminato ligands were synthesized and characterized. These complexes displayed high reactivity towards ortho-Csp(2)-H alkylation of 2-alkylpyridines and benzylic Csp(3)-H alkylation of 2,6-dialkylpyridines with alkenes, providing an atom-economical approach to alkylated pyridine derivatives. Mechanistic investigations revealed the catalytic cycle and enantioselectivity in the asymmetric version of Csp(3)-H alkylation.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Jingjing Liu, Jianxuan Shang, Jing Wei, Fangfang Gao, Lei Hou, Fanlong Zeng, Anyang Li, Wenyuan Wang
Summary: The synthesis and reactivity of a rigid alpha-diiminate ligand supported chlorogermylene 2 were demonstrated. Different reactions and reagents can produce germanium compounds with different properties and configurations.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Drew M. Hood, Ryan A. Johnson, David J. Vinyard, Frank R. Fronczek, George G. Stanley
Summary: HCo(CO)(x)(bisphosphine)](BF4), x = 1-3, is a highly active hydroformylation catalyst system, especially for internal branched alkenes. In situ spectroscopy studies provide evidence for the formation of a dicationic Co(I) paramagnetic CO-bridged dimer, which is derived from the reaction of two catalyst complexes. DFT studies reveal the structure of the dimer and EPR studies confirm the presence of a high-spin Co(II) complex in the catalyst.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Zhao Zhao, Jingjie Tan, Ting Chen, Zahid Hussain, Yanguo Li, Yile Wu, Douglas W. Stephan
Summary: This study investigates the reactions of germylene chloride and germylene thiocyanate with phenylacetylene and B(C6F5)3, leading to the formation of different products due to the difference in their reactant structures. The results provide insights into the reactivity and bonding of these compounds.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Vadim Zhuravlev, Przemyslaw J. Malinowski
Summary: Developments in the chemistry of weakly coordinating anions have led to the isolation of unique metal complexes with unusual ligands. In this paper, the synthesis and characterization of the first truly homoleptic {Cu[Fe(CO)(5)](2)}(+) cation as a salt of the weakly coordinating [Al(ORF)(4)](-) anion is presented. The results show that the stability of the complex is influenced by the selection of the proper anion and solvent.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Adriana Lugosan, Sophi R. Todtz, Andrew Alcazar, Matthias Zeller, James J. Devery, Wei-Tsung Lee
Summary: A series of air-stable trigonal bipyramidal Fe-III complexes supported by a redox non-innocent NNN pincer ligand were synthesized and characterized, with investigations on the interaction between acetone and the Fe-III center. The results revealed the presence of a high-spin ferric center and showed two quasi-reversible events in cyclic voltammetry studies. UV-Visible spectroscopy demonstrated ligand-metal charge transfer bands and coordination of acetone to the iron center.
Article
Chemistry, Multidisciplinary
Javier A. Cabeza, Javier F. Reynes, Felipe Garcia, Pablo Garcia-Alvarez, Ruben Garcia-Soriano
Summary: Iconic Lappert's heavier tetrylenes were efficiently prepared using a completely solvent-free mechanochemical route, representing a fast, high-yielding, and scalable approach with a small environmental footprint. This method is a rare example of the use of mechanochemistry in the realm of main group chemistry.
Article
Chemistry, Physical
Andreas Wolf, Andreas Zink, Lisa M. S. Stiegler, Robert Branscheid, Benjamin Apeleo Zubiri, Stephan Muessig, Wolfgang Peukert, Johannes Walter, Erdmann Spiecker, Karl Mandel
Summary: Most analytical techniques for studying the surface chemical properties of SPIONs are not suitable for in situ investigations in liquids. MPS can quickly resolve changes in magnetic interactions of SPIONs at ambient conditions. By adding cations to citric acid capped SPIONs, the degree of agglomeration can be used to study the selectivity of cations towards surface coordination motifs via MPS.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2023)
Article
Chemistry, Inorganic & Nuclear
Chisato Murata, Kyohei Kobayashi, Hiroshi Nakajima, Isamu Kinoshita, Sakie Sakai, Masakazu Hirotsu
Summary: The alkenyl- and thiolate-bridged diiron carbonyl complexes, derived from [Fe3(CO)12] and benzothiophenes, reacted with alkynes under photoirradiation conditions to form the acyl complexes. In this reaction, an alkyne and CO are inserted into the Fe-alkenyl bond, and the bulky substituents of alkynes occupy the R3 position.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Indresh Kumar Pandey, Tashika Agarwal, Shaikh M. Mobin, Matthias Stein, Sandeep Kaur-Ghumaan
Summary: This study demonstrates that by introducing a nitrogen base atom in the phosphine ligand, the reactivity of the active site can be significantly altered. Despite almost identical structural and spectroscopic properties, the addition of a nitrogen base atom in complex 2 leads to a marked change in site reactivity.
Article
Chemistry, Inorganic & Nuclear
Wanjie Ren, Charles E. Schulz, Mark H. Shroyer, Wei Xu, Shibo Xi, Pengfei An, Wenping Guo, Jianfeng Li
Summary: In this study, the electronic configurations of (nitrosyl)iron corroles with different para-substituted phenyl groups were investigated. Various techniques were employed to characterize these complexes and determine their electronic and magnetic properties. The study also established correlations between the electronic characteristics of the para-substituents and the electrochemical behavior and magnetic parameters of the complexes.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
M. A. Blagov, V. B. Krapivin, S. Simonov, N. G. Spitsyna
Summary: In this study, the relationship between the spin state of the Fe-III ion, conformations of the ethylene bridges in the ligand, and Fe-N/O bonds was analyzed based on literature data for 29 structures. It was found that the Fe-N-am and Fe-N-im bonds are most strongly influenced by the change in spin state, and the conformational switch of the ethylene bridges occurs within a specific range of gamma(HS).
RUSSIAN CHEMICAL BULLETIN
(2022)
Article
Chemistry, Physical
G. N. Altshuler, E. Ostapova, O. G. Altshuler
Summary: The study examines the equilibrium distribution of pyridine-3-carboxylic acid and iron(III) between an aqueous solution and sulfonic acid cation exchanger KU-2. Concentrations of individual components were calculated using the HySS 2009 program. Results showed that pyridine-3-carboxylic acid anions can form complex cations, and equilibrium constants were determined for ion exchange and ligand sorption in the system.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Chemistry, Multidisciplinary
Wei Li, Hechen Wu, Xunlei Ding, Xiaonan Wu
Summary: The cycloaddition reactions of methane and ethylene mediated by Ir+ have been studied using mass spectrometry and theoretical calculations. The results show that Ir+ can facilitate the cycloaddition reaction to generate a half-sandwich structure IrHCp+ including a pentamethylcyclopentadienyl ligand. The study provides insights into the reaction mechanism and may guide the design of new catalysts with improved selectivity and efficiency.
CHINESE CHEMICAL LETTERS
(2023)
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, Physical
Shihan Li, Xiao-Nan Wu, Shaodong Zhou
Summary: Gas-phase reactions of [OsC3](+) with methane at ambient temperature were studied using quadrupole-ion trap mass spectrometry combined with quantum chemical calculations. Comparison with product clusters revealed significant changes in cluster reactivity. Theoretical calculations showed that electronic features such as molecular polarity index, charge and spin distribution, and HOMO-LUMO gap had an influence on the reactivity of the Os complexes. The polarity of the clusters played a fundamental role in the methane activation. Lowering the local polarity of the catalyst active site may reduce the formation of byproducts in the reaction.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(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
Vaibhav Bedi, Dipendu Mandal, Zahid Hussain, Shi-Ming Chen, Yile Wu, Zheng-Wang Qu, Stefan Grimme, Douglas W. Stephan
Summary: The reaction of (tBuO(2)CN)(2) with 9-BBN leads to the formation of a bicyclic heterocyclic compound, while its reactions with BF3 or [Et3Si][B(C6F5)(4)] result in the isolation of different compounds. Computational studies reveal that the steric and electronic properties of the Lewis acid are important in the formation of one of the compounds.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Chisa Itoh, Haruka Yoshino, Taku Kitayama, Wataru Kosaka, Hitoshi Miyasaka
Summary: A new synthetic route for constructing functional paddlewheel diruthenium(II,II) complexes was developed, utilizing Schiff base condensation reactions. The attached Schiff base groups significantly affected the electronic states of the resulting complexes, as revealed by cyclic voltammetry and DFT calculations.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Danrui Ni, Haozhe Wang, Xianghan Xu, Weiwei Xie, Robert J. Cava
Summary: A layered rhombohedral polymorph of indium(iii) triiodide is synthesized at high pressure and temperature. It has an orange color, which is different from ambient pressure InI3, which has a monoclinic molecular structure and a light-yellow color.
DALTON TRANSACTIONS
(2024)
Review
Chemistry, Inorganic & Nuclear
Juan Carlos Perez-Sanchez, Raquel P. Herrera, M. Concepcion Gimeno
Summary: Gold(II) complexes have been less utilized in catalysis compared to their gold(I) and gold(III) counterparts. However, gold(II) complexes offer potential in homo-coupling and cross-coupling reactions, as they are more easily accessible through simplified oxidation and reduction processes. Gold(II) exhibits characteristics of both soft acid gold(I) and hard acid gold(III). This review explores the unique reactivity and potential applications of gold(II) species, highlighting their significance in catalytic transformations.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Nighat Yousuf, Yanping Ma, Qaiser Mahmood, Wenjuan Zhang, Yizhou Wang, Hassan Saeed, Wen-Hua Sun
Summary: In this study, a series of structurally rigid cyclooctyl-fused iminopyridine iron complexes were synthesized and used with methylaluminoxane for isoprene polymerization. The extent of steric hindrance of the ligand framework was found to significantly affect catalytic performance, with less hindrance leading to better activity and stability.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Chenghao Song, Huiwei Du, Menglei Xu, Jie Yang, Xinyu Zhang, Jungan Wang, Yuanfang Zhang, Chengjun Gu, Rui Li, Tao Hong, Jingji Zhang, Jiangying Wang, Yongchun Ye
Summary: This study improves the performance of perovskite solar cells by using a dual-hole transport layer strategy. This strategy enhances the charge transfer efficiency of the transport layer, reduces charge recombination, and improves the quality of the perovskite film layer. Ultimately, the stability of the device is enhanced.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Mahender Singh, Aakash Yadav, Ranjit Singh, Chullikkattil P. Pradeep
Summary: A new aryl selenonium polyoxometalate hybrid was developed and compared with an aryl sulfonium polyoxometalate hybrid in terms of their photocatalytic properties. It was found that the aryl selenonium hybrid exhibited better catalytic performance, which could be attributed to the larger atomic radii of selenium stabilizing the photogenerated electron-hole pair more efficiently. Additionally, the generation of elemental selenium through cleavage of C-Se bonds during catalysis was observed.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Yuhan Xie, Boyu Dong, Xuemin Wang, Siyuan Wang, Jinxi Chen, Yongbing Lou
Summary: This study successfully fabricated visible-light-responsive three-dimensional core-shell CoSe2/ZnIn2S4 heterostructures and achieved attractive activity in photocatalytic hydrogen evolution. The presence of CoSe2 improved light absorption and accelerated charge transfer kinetics. The strong interaction between CoSe2 and ZnIn2S4 reduced charge recombination, further enhancing photocatalytic activity for hydrogen evolution.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Andre L. de O. Batista, Joao Marcos T. Palheta, Mauricio J. Piotrowski, Celso R. C. Rego, Diego Guedes-Sobrinho, Alexandre C. Dias
Summary: This study presents a simulation protocol that provides a solid foundation for exploring two-dimensional materials. Using the TiBr2 2H monolayer as an example, the study reveals its promising properties for optoelectronic and valleytronic applications, including its stability, spin-orbit coupling effects, and optical helicity selection rule.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Jiang Jiang, Zi-Wei Li, Zhi-Zhuan Zhang, Bin Tan, Zhao-Feng Wu, Xiao-Ying Huang
Summary: In this work, two metal organic frameworks (MOFs) containing {Cu2I2} clusters, Eu-CuI-INA and Sr-K-CuI-INA, were synthesized and characterized. Both materials have a three-dimensional structure with {Cu2I2} clusters coordinated by INA(-) ligands and Eu3+ or Sr2+ ions. The Sr-K-CuI-INA material exhibited sensitive fluorescence sensing behaviors towards cysteine and nitro-bearing molecules, showing potential applications in bio and explosive molecule sensing. This work provides a good reference for designing fluorescent MOF probes containing CuI molecules.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Zhiya Lin, Jiasheng Wu, Qianwen Ye, Yulong Chen, Hai Jia, Xiaohui Huang, Shaoming Ying
Summary: Na-ion batteries (NIBs) have attracted great interest as a potential technology for grid-scale energy storage due to the wide distribution, low cost, and environmental friendliness of sodium resources. However, their implementation is hindered by low rate capability and cycling stability caused by the large ionic size of Na+. In this study, a three-dimensional nanoarchitectured coral-like CoSe2@N-doped carbon (CL-CoSe2@NC) was synthesized, and it exhibited improved sodium storage properties with better electrode kinetics and a stable SEI film.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Ya-Qiong Zhang, Yu Zhang, Guoping Zeng, Rong-Zhen Liao, Man Li
Summary: The mechanism and selectivity of CO2 reduction under visible light were investigated using density functional calculations. The results showed that a tetradentate PNNP-type Iridium(III) complex exhibited high activity and selectivity in the reaction.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Sanyukta Ghosh, Shubhanth Jain, Soumya Ranjan Mishra, Gerda Rogl, Peter Rogl, Ernst Bauer, B. S. Murty, A. Govindaraj, Ramesh Chandra Mallik
Summary: In this study, reduced graphene oxide (rGO) was uniformly dispersed in the In0.5Co4Sb12 bulk material by ultrasonication, which effectively reduced the lattice thermal conductivity and improved the thermoelectric efficiency.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Mika Takeuchi, Yutaka Amao
Summary: This study developed an effective visible-light driven system for fumaric acid production using renewable resources such as biomass derivatives, providing an alternative to the current petroleum-based synthesis methods.
DALTON TRANSACTIONS
(2024)
Article
Chemistry, Inorganic & Nuclear
Juan Jian, Meiting Wang, Zhuo Wang, Jingwen Meng, Yuqin Yang, Limin Chang
Summary: Developing low-cost and self-supported bifunctional catalysts is crucial for highly efficient water splitting devices. In this study, nano-NiFe2O4 was directly grown onto iron foil surface and Sn4+ was introduced into the NiFe2O4. The resulting Sn-NiFe2O4/IF showed low overpotentials and high current densities during oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), making it a promising catalyst for large-scale hydrogen production.
DALTON TRANSACTIONS
(2024)
