European Journal of Inorganic Chemistry最新文献

{"title":"Solid-State Structures of Three Zinc(II) Coordination Polymers with 3-(1H-Imidazol-1-yl)propanoate Linkers Prepared in Water","authors":"Katharina Kodolitsch,&nbsp;Ana Torvisco,&nbsp;Tomas Kamencek,&nbsp;Matjaž Mazaj,&nbsp;Egbert Zojer,&nbsp;Christian Slugovc","doi":"10.1002/ejic.202500032","DOIUrl":"https://doi.org/10.1002/ejic.202500032","url":null,"abstract":"<p>Coordination polymers of zinc(II) with three readily accessible 3-(1H-imidazol-1-yl)propanoate ligands are prepared by combining aqueous solutions of the ligands and zinc(II) salts, resulting in a precipitation of the respective coordination polymers. While sodium 3-(1H-imidazol-1-yl)propanoate and sodium 3-(2-phenyl-1H-imidazol-1-yl)propanoate initially yield amorphous precipitates that can be converted to crystalline materials upon prolonged heating, the use of sodium 3-(2-methyl-1H-imidazol-1-yl)propanoate results in the immediate formation of a crystalline coordination polymer. All three coordination polymers are structurally characterized by single-crystal X-ray diffraction. The crystal water in one coordination polymer can be removed without losing the crystallinity of the sample and this process is studied by infrared spectroscopy. The interpretation of the corresponding infrared spectra is supported by theoretical calculations. Furthermore, the solubility in water and buffer solutions and the potential porosity of the coordination polymers are investigated, revealing their nonporous character for CO₂, N₂, and CH₄.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 17","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500032","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144308728","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Thermochemistry of cis trans isomerization in MCl2L2(PPh3)2, M=Ru, Os; L=CO, CNCH2SO2-p-tolyl.","authors":"Philip J. Karageorghis,&nbsp;Amalia S. Baikie,&nbsp;D. Scott Bohle","doi":"10.1002/ejic.202500097","DOIUrl":"https://doi.org/10.1002/ejic.202500097","url":null,"abstract":"<p>Ten neutral dichlorobistriphenylphosphine complexes of ruthenium(II) and osmium(II) with two π-accepting ligands, CO or CNCH₂SO₂-<i>p</i>-tolyl (TosMIC), have been prepared and characterized. There are five pairs of complexes, each with <i>trans</i>-triphenylphosphines and either <i>cis</i> or <i>trans</i> arrangement of the two chlorides and two π-accepting ligands. The all-<i>trans</i> arrangement, <i>ttt</i>-MCl₂L₂(PPh₃)₂ are prepared under kinetic control by adding 2 L to MCl₂(PPh₃)₃. In most cases these can be stoichiometrically thermally isomerized to the more thermodynamically stable <i>cct</i>-MCl₂L₂(PPh₃)₂ as either a solid or in solution with high boiling solvent. Mixed carbonyl/isocyanide complexes form by treating ttt-MCl₂(CO)₂(PPh₃)₂ with excess isocyanide at room temperature to give ttt-MCl₂(CO)(CNR)(PPh₃)₂ with retention of stereochemistry at the metal. Thermolysis of these mixed species also cleanly transform to the thermodynamically stable <i>cct</i>-isomers. Differential scanning calorimetry is used to determine the temperature onset (155–229 °C) and enthalpy (19–92 J/mol) for these isomerizations. In examples with at least one CO ligand, these DSC methods allow for Borchardt-Daniels kinetics determination of the energy of activations for these isomerizations between 169–282 kJ/mol. Single crystal X-ray diffraction confirms the spectroscopically assigned geometries and DFT calculations of the most likely intermediates for carbonyl substitution in ttt-MCl₂(CO)₂(PPh₃)₂ supports carbonyl loss as the initial step in these substitution reactions. It is proposed that isomerization competes with geminate recombination of the dissociated CO or CNR to give the starting isomer ttt-MCl₂L₂(PPh₃)₂.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 14","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500097","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144131527","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structure and Aromaticity of Germabenzenes: A Computational Investigation","authors":"Bitupon Borthakur,&nbsp;Bijoy Ghosh,&nbsp;Shahnaz Sultana Rohman,&nbsp;Susmita Chetia,&nbsp;Biraj Das,&nbsp;Eramoni Saikia","doi":"10.1002/ejic.202500121","DOIUrl":"https://doi.org/10.1002/ejic.202500121","url":null,"abstract":"<p>Quantum chemical calculations are carried out to investigate the structures and stability of a variety of germabenzenes. In addition, an attempt is also made to study the aromatic ring current present in these germanium analogs of benzene. Interestingly, computed nucleus-independent chemical shift values indicate the presence of significant aromatic character in the hexagermabenzene.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 17","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144308876","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Experimental and Computational Studies of Amido Chlorogermylenes as Lewis Acids in CO2 Insertion","authors":"Jussi Lundahl,&nbsp;Dr. Laura E. English,&nbsp;Dr. Jas S. Ward,&nbsp;Dr. Petra Vasko","doi":"10.1002/ejic.202500116","DOIUrl":"https://doi.org/10.1002/ejic.202500116","url":null,"abstract":"<p>A novel combination of an amido-stabilised chlorogermylene (RGeCl) and a cyclic (alkyl)(amino)carbene (cAAC) has been utilized in a frustrated Lewis pair-type reaction to activate and capture CO₂. The synthesis, characterization, and reactivity studies accompanied by extensive computational input reveal “push-pull”-type interactions in the isolated CO₂-captured compounds. Both the steric and electronic factors as well as the Lewis acidity/basicity are found to play an important role in the reactivity and ability of the FLPs to activate CO₂. The results indicate that the covalent interaction between the cAAC carbene carbon and electrophilic CO₂-carbon is too strong to facilitate further reduction or reactivity of the bound CO₂-moiety. However, the interaction between the Lewis acidic Ge-species and the nucleophilic O-atom of CO₂ shows that germylenes can be utilised as the Lewis acidic partner in FLP-type chemistry and small molecule activation.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 14","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500116","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144131576","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Front Cover: Ecofriendly Synthesis of Titanium Dioxide for Glyphosate Adsorption (Eur. J. Inorg. Chem. 8/2025)","authors":"Eleonora Marconi,&nbsp;Alberto Lopez,&nbsp;Federica Bertelà,&nbsp;Carlo Meneghini,&nbsp;Chiara Battocchio,&nbsp;Daniele Mirabile Gattia,&nbsp;Giuseppina Vanga,&nbsp;Paolo Centomo,&nbsp;Marco Zecca,&nbsp;Valentina Rizzotto,&nbsp;Silvia Pettenuzzo,&nbsp;Marco Roverso,&nbsp;Sara Bogialli,&nbsp;Ulrich Simon,&nbsp;Peirong Chen,&nbsp;Luca Tortora","doi":"10.1002/ejic.202580801","DOIUrl":"https://doi.org/10.1002/ejic.202580801","url":null,"abstract":"<p><b>The Front Cover</b> highlights titanium dioxide nanoparticles with distinct crystalline phases, essential for efficient glyphosate adsorption. TiO₂ nanoparticles are also depicted within a mesoporous framework to emphasize their structural influence on adsorption performance. The interaction of glyphosate molecules with the nanoparticle surfaces, set against a water-inspired backdrop, underscores the environmental application and significance of tailored crystalline phases in optimizing remediation strategies. More information can be found in the Research Article by L. Tortora and co-workers.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 8","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202580801","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143645786","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Development of 2-Bis(Quinolin-2-Ylmethylene)Hydrazine-Based Half-Sandwich Ruthenium(II) Arene Complexes with High Cytotoxicity in Castration-Resistant Prostate Cancer Cells","authors":"Tanveer A. Khan,&nbsp;Anubha Yadav,&nbsp;Priyal Malpani,&nbsp;Vinit Kumar,&nbsp;Anuj K. Sharma","doi":"10.1002/ejic.202400851","DOIUrl":"https://doi.org/10.1002/ejic.202400851","url":null,"abstract":"<p>Metal complexes that can target uncurable forms of cancer are in high demand. Presented herein is detailed characterization, anticancer activity and structure–activity comparison for a set of Ru(II) arene chlorido organometallic complexes [(η⁶-arene)(L)RuCl]PF₆ (<b>BzRuL</b> and <b>HmbRuL</b>) using 2-bis(quinolin-2-ylmethylene) hydrazine (<b>L</b>) as ligand. <b>BzRuL</b> and <b>HmbRuL</b> was characterized by elemental analyses, FTIR, ¹H, ¹³C-NMR, ¹H–¹H COSY-NMR, and ESI mass spectroscopy. Spectroscopic and single-crystal X-ray diffraction (XRD) analysis suggested that the complexes <b>BzRuL</b> and <b>HmbRuL</b> exhibit a piano-stool structure. These complexes exhibit potent anticancer activity (IC₅₀ 9.62 μM for <b>BzRuL</b> and 7.23 μM for <b>HmbRuL</b>) even more effective than the standard drug cisplatin in a castration-resistant human prostatic adenocarcinoma cell line (PC-3). Their comparative analysis with our recently reported highly active Ru(II) complex with same ligand <b>pCYRuL</b> (IC₅₀ 0.71 μM) is also presented. Both the complexes interact with dsDNA and likely induce apoptosis via DNA damage pathway. This study introduces a new family of Ru complexes with promising potential for preclinical development against incurable prostate cancer.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 17","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144309085","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Heterometallic Coordination Compounds with Amino-Acid Dithiocarbamate Ligands","authors":"Dr. Phil Köhler","doi":"10.1002/ejic.202500007","DOIUrl":"https://doi.org/10.1002/ejic.202500007","url":null,"abstract":"<p>Dithiocarbamates derived from amino acids (AA-DTCs) are synthetically easily available O,S-ditopic ligands that are potentially able to coordinate to a hard, oxophilic and to a soft, thiophilic metal site selectively, making them suitable as building blocks for heterobimetallic coordination compounds. When an AA-DTC anion is treated with a transition metal ion (M1), usually a sulfur-coordinate complex of defined geometry is formed widely uninfluenced by the oxygen functional group. The carboxylate group is capable to bind a second metal M2, where the carboxylate-M2 linkage has a more ionic character and the coordination around M2 is characterized by carboxylate/solvent competition. In the vast majority of known compounds, the building blocks are linked into infinite assemblies of different dimensions. This comprehensive review surveys the synthesis and molecular structures of heterobimetallic compounds with AA-DTC anions, comprising different salt-like compounds of the highly oxophilic closed-shell metal ions of groups 1–3, coordination polymers and networks for the first-row transition metal ions, as well as highly covalent compounds with p-block metal fragments as the oxophilic component.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 13","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500007","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144108975","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structural Diversity of Iron Complexes Based on Chelating 5,5′-dimethyl-2,2′-bipyridine Ligand","authors":"Jana Tomičová,&nbsp;Matiková Maľarová,&nbsp;Juraj Kuchár,&nbsp;Erika Samolova,&nbsp;Jaroslav Briančin,&nbsp;Juraj Černák","doi":"10.1002/ejic.202500127","DOIUrl":"https://doi.org/10.1002/ejic.202500127","url":null,"abstract":"<p>Using different synthetic procedures, four complexes [Fe₂Cl₄(<i>5dmbpy</i>)₂] (<b>1</b>), [Fe(<i>acac</i>)Cl₂(<i>5dmbpy</i>)] (<b>2</b>), [Fe(<i>5dmbpy</i>)₃][Fe₂Cl₆O] (<b>3</b>), and [Fe(<i>5dmbpy</i>)₃][Fe₂Cl₆O]·CH₃CN (<b>4</b>) (<i>5dmbpy</i> is 5,5′-dimethyl-2,2′-bipyridine; <i>acac</i> is acetylacetonate) are prepared and characterized. Complex <b>1</b> is built up of dinuclear molecules in which two pentacoordinate Fe(II) atoms are linked by a pair of chloride ligands and coordination is completed by chelating <i>5dmbpy</i> and terminal chloride ligand. Complex <b>2</b> exhibits a molecular structure in which the hexacoordination of the Fe(III) is achieved by chelating <i>5dmbpy</i> and <i>acac</i> ligands and two chloride ligands. Complexes <b>3</b> and <b>4</b> exhibit ionic structures and they are built up of [Fe(<i>5dmbpy</i>)₃]²⁺ complex cation and dinuclear complex anion [Cl₃FeOFeCl₃]²⁻ in which Fe(III) atoms are bridged by a μ-oxido ligand. Complex <b>4</b> contains an additional acetonitrile solvate molecule. The crystal structures are stabilized by weak hydrogen interactions <b>2</b>–<b>4</b> and π–π stacking interactions <b>1</b>. Complex <b>1</b> is stable up to a temperature of 180 °C and complex <b>4</b> up to 160 °C, while complexes <b>2</b> and <b>3</b> display higher thermal stabilities up to 240 °C. The solid residues of the thermal decompositions of <b>1</b>–<b>3</b> at 800 °C are formed by <i>α</i>-Fe₂O₃ as corroborated by a combination of X-ray powder diffraction, scanning electron microscope, and energy-dispersive X-ray spectroscopy.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 20","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144647526","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring the Synergistic Electrochemical Benefits of a Niobium-Doped MoO3/Ta2O5 Catalyst for an Enhanced Oxygen Evolution Reaction","authors":"Mange Ram,&nbsp;Ayan Roy,&nbsp;Krishna Kanta Haldar","doi":"10.1002/ejic.202400681","DOIUrl":"https://doi.org/10.1002/ejic.202400681","url":null,"abstract":"<p>This study delves into the synergistic electrochemical advantages of a niobium-doped molybdenum trioxide (MoO₃) nanorods combined with a tantalum pentoxide (Ta₂O₅) catalyst to increase the efficiency of the oxygen evolution reaction (OER). In light of the increasing demand for sustainable energy solutions, the imperative to develop efficient electrocatalysts conducive to water splitting, a critical process in hydrogen production, becomes evident. This investigation involves the synthesis of a niobium-doped MoO₃/Ta₂O₅ composite and comprehensively evaluating its structural, electrochemical, and catalytic properties through various spectroscopic and electrochemical techniques. These findings highlight that incorporating niobium markedly enhances the electronic conductivity and availability of active sites within the catalyst, resulting in improved OER performance. Comparative analyses against conventional electrocatalysts underscore that the 8% niobium-doped MoO₃/Ta₂O₅ composite demonstrates lower overpotentials (238 mV ) and higher current densities, indicating its significant potential for practical applications. Furthermore, the robust metal–support interactions enabled by the Ta₂O₅ support stabilize the active phase and increase the catalyst's overall durability. This work yields valuable insights into the mechanisms of OER catalysis involving niobium-doped metal oxides, thereby underscoring the potential of such innovative catalyst designs in advancing hydrogen production technologies.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 17","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144308913","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Pyrazolyl-Pyridine Ruthenium (II) Catalysts for Selective Hydrogen Generation Through Formic Acid Dehydrogenation","authors":"Rotondwa Mphephu,&nbsp;M. Cassiem Joseph,&nbsp;Andrew John Swarts","doi":"10.1002/ejic.202500063","DOIUrl":"https://doi.org/10.1002/ejic.202500063","url":null,"abstract":"<p>A series of pyridine-pyrazolyl Ru(II) p-cymene complexes of the type [RuCl(p-cymene)<b>L</b>]X (<b>C1</b>–<b>C7</b>, X = Cl, BPh₄ or PF₆), featuring different electronic and steric properties, are prepared by the reaction of 3,5-disubstituted pyrazolyl-pyridine ligands (<b>L1</b>–<b>L3</b>) with [Ru(<i>p</i>-cymene)Cl₂]₂ followed by salt metathesis with NaBPh₄ or AgPF₆. The complexes, upon activation with formate, show activity toward the dehydrogenation of formic acid (FA) to produce equimolar quantities of H₂ and CO₂. In optimization studies, kinetic and thermodynamic investigations provide insight into the role of pre-catalyst and FA in the catalytic process. It is demonstrated that the most active catalyst derived from <b>C4</b>, could dehydrogenate FA to CO₂ and H₂ in quantitative yields within 1 h with tons and TOFs of ≈1032 and ≈1238 h⁻¹, respectively. Reactivity patterns are rationalized based on electronic properties and our understanding of ion pairing in related compounds. Reactivity studies between <b>C4</b> and HCOOK provide evidence for the key Ru-monohydride species involved in catalysis.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 18","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500063","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144473075","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}