Inorganic Chemistry最新文献

The Alkylation of Phenol with Methanol: The Influence of Acid–Base Properties of X Zeolite on the Selectivity of para- and meta-Cresol

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2024-12-23 DOI: 10.1021/acs.inorgchem.4c04101

Lei Li, Xianlong Gao, Fangtao Huang, Lei Miao, Guoqing Zhao, Zhirong Zhu

{"title":"The Alkylation of Phenol with Methanol: The Influence of Acid–Base Properties of X Zeolite on the Selectivity of para- and meta-Cresol","authors":"Lei Li, Xianlong Gao, Fangtao Huang, Lei Miao, Guoqing Zhao, Zhirong Zhu","doi":"10.1021/acs.inorgchem.4c04101","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04101","url":null,"abstract":"The vapor-phase alkylation of phenol with methanol was investigated on X zeolites and modified X zeolites. First, the difference of product distribution was tested between acid zeolite (HZSM-5, HX, HMCM-22, and Hβ) and basic zeolite X (KX and CsX). Then, X zeolites were modified with Li, K, Cs, Ca, Mg, La, and Ce ion exchange to adjust the acid–base properties of the zeolites. Finally, the type of acid sites and strength of acid–base sites on zeolite catalysts were determined by characterization techniques such as Py-IR and TPD, and the alkylation of phenol with methanol was tested. The results showed that O-alkylation products convert to the C-alkylation products on the B acid sites, which enhances the isomerization reaction, thereby increasing the proportion of meta-cresol in cresol. The results of TPD and IR indicated that weak basic sites on the zeolite promote the vertical adsorption of the aromatic ring and strong basic sites promote side-chain activation, while acid sites determine whether ring substitution or side-chain substitution occurs. During the reaction of phenol with methanol, the phenolic hydroxyl group strongly interacts with the surface of zeolites, leading to differences in the adsorption mode of the aromatic ring (vertical or parallel), which, in turn, alters the position of alkyl substitution. It is found that the proper acid–base property of X zeolites can selectively determine the desired alkylated products.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"92 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874292","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Cisplatin/Apo-Transferrin Adduct: X-ray Structure and Binding to the Transferrin Receptor 1

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2024-12-23 DOI: 10.1021/acs.inorgchem.4c04435

Romualdo Troisi, Francesco Galardo, Giarita Ferraro, Rosanna Lucignano, Delia Picone, Alessandra Marano, Marco Trifuoggi, Filomena Sica, Antonello Merlino

引用次数: 0

Force-Activated Spin-Crossover in Fe2+ and Co2+ Transition Metal Mechanophores

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2024-12-23 DOI: 10.1021/acs.inorgchem.4c04732

Xiao Huang, Ilia Kevlishvili, Stephen L. Craig, Heather J. Kulik

{"title":"Force-Activated Spin-Crossover in Fe2+ and Co2+ Transition Metal Mechanophores","authors":"Xiao Huang, Ilia Kevlishvili, Stephen L. Craig, Heather J. Kulik","doi":"10.1021/acs.inorgchem.4c04732","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04732","url":null,"abstract":"Transition metal mechanophores exhibiting force-activated spin-crossover are attractive design targets, yet large-scale discovery of them has not been pursued due in large part to the time-consuming nature of trial-and-error experiments. Instead, we leverage density functional theory (DFT) and external force explicitly included (EFEI) modeling to study a set of 395 feasible Fe2+ and Co2+ mechanophore candidates with tridentate ligands that we curate from the Cambridge Structural Database. Among nitrogen-coordinating low-spin complexes, we observe the prevalence of spin crossover at moderate force, and we identify 155 Fe2+ and Co2+ spin-crossover mechanophores and derive their threshold force for low-spin to high-spin transition (FSCO). The calculations reveal strong correlations of FSCO with spin-splitting energies and coordination bond lengths, facilitating rapid prediction of FSCO using force-free DFT calculations. Then, among all Fe2+ and Co2+ spin-crossover mechanophores, we further identity 11 mechanophores that combine labile spin-crossover and good mechanical robustness that are thus predicted to be the most versatile for force-probing applications. We discover two classes of mer-symmetric complexes comprising specific heteroaromatic rings within extended π-conjugation that give rise to Fe2+ mechanophores with these characteristics. We expect the set of spin-crossover mechanophores, the design principles, and the computational approach to be useful in guiding the high-throughput discovery of transition metal mechanophores with diverse functionalities and broad applications, including mechanically activated catalysis.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"61 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874285","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Water Oxidation in the Presence of Iron-Doped Copper (Hydr)Oxide

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2024-12-23 DOI: 10.1021/acs.inorgchem.4c04610

Mohammad Saleh Ali Akbari, Subhajit Nandy, Pavlo Aleshkevych, Keun Hwa Chae, Mohammad Mahdi Najafpour

{"title":"Water Oxidation in the Presence of Iron-Doped Copper (Hydr)Oxide","authors":"Mohammad Saleh Ali Akbari, Subhajit Nandy, Pavlo Aleshkevych, Keun Hwa Chae, Mohammad Mahdi Najafpour","doi":"10.1021/acs.inorgchem.4c04610","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04610","url":null,"abstract":"This study explores the influence of Fe ion incorporation on the oxygen-evolution reaction (OER) in alkaline media, utilizing CuO-based materials. Instead of developing an efficient and stable OER catalyst, this research investigates two distinct CuO variants: one with Fe ions adhered to the surface and another with Fe ions integrated into the CuO lattice. By employing a variety of analytical techniques, the study demonstrates that the CuO variant with surface-bound Fe ions (referred to as compound 1) exhibits significantly enhanced OER performance compared to the variant with internally embedded Fe ions (referred to as compound 2). The Tafel plots obtained from multistep amperometry profiles for compounds 1 and 2, as well as pure CuO and FeO(OH), exhibit linear relationships in the log(j) vs overpotential plot, with Tafel slopes of 39.3, 41.5, 115.9, and 121.9 mV/decade, respectively. These Tafel slopes indicate that compounds 1 and 2 likely share a similar reaction mechanism, whereas CuO and FeO(OH) appear to follow distinct mechanisms. At 570 mV overpotential, the turnover frequencies of Fe ions for compounds 1 and 2, as well as for FeO(OH), calculated from electrode compositions and chronoamperometry data, are found to be 1.1, 0.2, and 5.7 × 10–4 s–1, respectively. Despite the differing distributions of Fe ions, both CuO variants exhibit similar Tafel slopes, suggesting that they follow comparable OER mechanisms. Additionally, cyclic voltammetric profiles, corrected for the electrochemically active surface area, indicate that FeO(OH) demonstrates notably higher activity than the other compounds. These findings deepen our understanding of Fe’s role in CuO structures for OER processes and offer valuable insights for the design of more efficient electrocatalytic materials in alkaline environments.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"80 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874284","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Uranyl Speciation in Carbonate-Rich Hydrothermal Solutions: A Molecular Dynamics Study

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2024-12-23 DOI: 10.1021/acs.inorgchem.4c04147

Xi Zhang, Xiandong Liu, Yingchun Zhang, Tianhua Wang, Pengyuan Gao, Xiancai Lu

{"title":"Uranyl Speciation in Carbonate-Rich Hydrothermal Solutions: A Molecular Dynamics Study","authors":"Xi Zhang, Xiandong Liu, Yingchun Zhang, Tianhua Wang, Pengyuan Gao, Xiancai Lu","doi":"10.1021/acs.inorgchem.4c04147","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04147","url":null,"abstract":"In this study, we employed classical molecular dynamics (CMD) and first-principles molecular dynamics (FPMD) simulations to investigate the speciation of uranyl in carbonate-rich hydrothermal solutions. The association constants (log10KA) of uranyl carbonate complexes were derived from the potential of mean forces (PMFs) obtained from CMD simulations, and the acid constants (pKas) of uranyl aqua ions were calculated using the FPMD-based vertical energy gap method. The results showed that uranyl ions could form stable mono- and bi-carbonate complexes at elevated temperatures and that uranyl aqua ions strongly hydrolyzed in neutral solutions at temperatures exceeding 473 K. The speciation of uranyl in hydrothermal solutions was constructed based on the calculated thermodynamics data. It was found that uranyl carbonate complexes were predominant in aqueous solutions at temperatures below 373 K, and at higher temperatures, UO2(OH)2/UO2(OH)+ became the predominant species. These findings provide molecular-level insight into the speciation of uranyl in hydrothermal solutions and highlight the role of uranyl hydroxides in the transport and deposition of uranium in hydrothermal processes.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"26 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874224","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Assembly of the Skirt-Like Giant Molybdenum Blue Cluster {Mo158} from Dimerization of {Mo79} Featuring an Octameric Skeleton

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2024-12-23 DOI: 10.1021/acs.inorgchem.4c04168

Hui-Min Zeng, Mengyuan Cheng, Weimin Xuan, Yongge Wei

{"title":"Assembly of the Skirt-Like Giant Molybdenum Blue Cluster {Mo158} from Dimerization of {Mo79} Featuring an Octameric Skeleton","authors":"Hui-Min Zeng, Mengyuan Cheng, Weimin Xuan, Yongge Wei","doi":"10.1021/acs.inorgchem.4c04168","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04168","url":null,"abstract":"Cyclic compounds are appealing owing to their intrinsic porous structures and facile accessibility as building blocks (BBs) for fabricating high-order assemblies. Nevertheless, the modular synthesis of such molecular entities and their subsequent controlled assembly are still very challenging. Herein, we report the synthesis of a gigantic molybdenum blue (MB) wheel {Mo158} (1), featuring a skirt-shaped structure dimerized from {Mo79}. {Mo79} exhibits an unprecedented octameric architecture built from eight sets of {Mo8} BBs, and the controlled assembly of this smallest member in the MB library is achieved by proper wheel contraction induced by {Mo1} and edge-sharing {Mo2} BBs. Moreover, {Mo158} can function as a 4-connected giant synthon, connecting with adjacent four clusters in a controlled manner via four Mo–O–Mo bridges, resulting in a high-order architecture with a 2D layer structure. In addition to single-crystal X-ray diffraction, {Mo158} is fully characterized by a variety of spectroscopies, allowing for the unambiguous determination of its structure and formula. This work not only enriches the family of gigantic clusters but also demonstrates their potential for constructing more complex assemblies.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"281 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874282","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Cross-Dehydrogenative Coupling of Secondary Amines with Silanes Catalyzed by Agostic Iridium-NSi Species

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2024-12-22 DOI: 10.1021/acs.inorgchem.4c04512

Marina Padilla, María Batuecas, Pilar García-Orduña, Israel Fernández, Francisco J. Fernández-Álvarez

{"title":"Cross-Dehydrogenative Coupling of Secondary Amines with Silanes Catalyzed by Agostic Iridium-NSi Species","authors":"Marina Padilla, María Batuecas, Pilar García-Orduña, Israel Fernández, Francisco J. Fernández-Álvarez","doi":"10.1021/acs.inorgchem.4c04512","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04512","url":null,"abstract":"An active catalytic system for the cross-dehydrogenative coupling (CDC) of a wide range of secondary amines with silanes is reported. The iridium(III) derivatives [Ir(H)(X)(κ2-NSiDMQ)(L)] (NSiDMQ = {4,8-dimethylquinoline-2-yloxy}dimethylsilyl; L = coe, X = Cl, 2; L = coe, X = OTf, 3; L = PCy3, X = Cl, 4; L = PCy3, X = OTf, 5), which are stabilized by a weak yet noticeable Ir···H–C agostic interaction between the iridium and one of the C–H bonds of the 8-Me substituent of the NSiDMQ ligand, have been prepared and fully characterized. These species have proven to be effective catalysts for the CDC of secondary amines with hydrosilanes. The best catalytic performance (TOF1/2 = 79,300 h–1) was obtained using 5 (0.25 mol %), N-methylaniline, and HSiMe2Ph. The catalytic activity of the species [Ir(H)(OTf)(κ2-NSiQ)(PCy3)] (10, NSiQ = {quinoline-2-yloxy}dimethylsilyl) and [Ir(H)(OTf)(κ2-NSiMQ)(PCy3)] (11, NSiMQ = {4-methylquinoline-2-yloxy}dimethylsilyl), related to 5 but lacking the 8-Me substituent, is markedly lower than that found for 5. This fact highlights the crucial role of the 8-Me substituent of the NSiDMQ ligand in enhancing the catalytic performance of these iridium complexes.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"125 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874286","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Synthesis and Stability of High-Energy-Density Niobium Nitrides under High-Pressure Conditions

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2024-12-21 DOI: 10.1021/acs.inorgchem.4c03331

Huawei Chen, Maxim Bykov, Iskander G. Batyrev, Lukas Brüning, Elena Bykova, Mohammad F. Mahmood, Stella Chariton, Vitali B. Prakapenka, Timofey Fedotenko, Konstantin Glazyrin, Mohamed Mezouar, Gaston Garbarino, Andrew Steele, Alexander F. Goncharov

引用次数: 0

Synthesis of Hollowed Polyoxometalate with a Flipped VO5 Unit by the Elimination of a Centered Organic Molecule

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2024-12-21 DOI: 10.1021/acs.inorgchem.4c04682

Yuji Kikukawa, Mayumi Taga, Yusuke Horikawa, Ryoji Mitsuhashi, Yoshihito Hayashi

{"title":"Synthesis of Hollowed Polyoxometalate with a Flipped VO5 Unit by the Elimination of a Centered Organic Molecule","authors":"Yuji Kikukawa, Mayumi Taga, Yusuke Horikawa, Ryoji Mitsuhashi, Yoshihito Hayashi","doi":"10.1021/acs.inorgchem.4c04682","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04682","url":null,"abstract":"Mechanistic understanding of the formation of clusters plays a role in designing the structure-dependent properties. Based on the fact that anions act as templates to form spherical polyoxovanadates, various structures were reported by changing anions in the synthetic solution. In this work, another factor in the formation of spherical polyoxometalates was demonstrated. By the reaction of [V10O26]4– in acetonitrile with a reductant to increase the number of tetravalent V4+ and p-toluene sulfonic acid to convert tetrahedral VO4 units to square-pyramidal VO5, acetonitrile-containing polyoxovanadate [V24O60(CH3CN)]6– (ICH3CN) was synthesized. The bulky and hydrophobic aromatic rings prevented the formed anions from acting as a template. By changing the synthetic solvent, encapsulated moieties were controlled. Nitromethane was also encapsulated to afford [V24O60(CH3NO2)]6– (ICH3NO2). When acetone was used as the solvent, the contaminated water was encapsulated to form [V24O60(H2O)]6– (IH2O). The encapsulated acetonitrile molecule was eliminated by heating ICH3CN up to 230 °C under N2 flow conditions to give hollowed polyoxovanadate [V24O60]6– (II), even though ICH3CN possesses no pores for acetonitrile to pass. From the X-ray crystallographic analysis of II, one of the 24 VO5 units was flipped. The electrochemical properties and catalytic performances between ICH3CN and II were also investigated.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"29 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142867493","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Dinuclear Rare-Earth β-Diketiminates with Bridging 3,5-Ditert-butyl-catecholates: Synthesis, Structure, and Single-Molecule Magnet Properties

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2024-12-21 DOI: 10.1021/acs.inorgchem.4c03278

Svetlana V. Klementyeva, Michael T. Gamer, Michael Schulze, Nithin Suryadevara, Artem S. Bogomyakov, Pavel A. Abramov, Sergey N. Konchenko, Mario Ruben, Wolfgang Wernsdorfer, Eufemio Moreno-Pineda

{"title":"Dinuclear Rare-Earth β-Diketiminates with Bridging 3,5-Ditert-butyl-catecholates: Synthesis, Structure, and Single-Molecule Magnet Properties","authors":"Svetlana V. Klementyeva, Michael T. Gamer, Michael Schulze, Nithin Suryadevara, Artem S. Bogomyakov, Pavel A. Abramov, Sergey N. Konchenko, Mario Ruben, Wolfgang Wernsdorfer, Eufemio Moreno-Pineda","doi":"10.1021/acs.inorgchem.4c03278","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03278","url":null,"abstract":"The dinuclear β-diketiminato complex [L1ClDy(μ-Cl)3DyL1(THF)] (1) (L1 = {2,6-iPr2C6H3–NC(Me)CHC(Me)N-2,6-iPr2C6H3}−) was obtained by reaction of DyCl3 with KL1 in a molar ratio of 1:1 and used for the preparation of the mixed-ligand complex [L1Dy(μ-3,5-Cat)]2 (2) by salt metathesis reaction with 3,5-CatK2 (3,5-Cat −3,5-di-tert-butyl-catecholate). Reactions of 3,5-CatNa2 with [L2LnCl2(THF)2] (Ln3+ = Dy, Y) ligated with the less bulky ligand L2 = {2,4,6-Me3C6H2–NC(Me)CHC(Me)N-2,4,6-Me3C6H2}− afforded the mixed-ligand THF-containing complexes [L2Ln(μ-3,5-Cat)(THF)]2 (Ln3+ = Dy (3a), Y (3b)). All new complexes were fully characterized, and the solid-state structures were determined by single-crystal X-ray diffraction. Magnetic measurements revealed single-molecule magnet behavior for the dysprosium complexes. Sub-Kelvin μSQUID studies confirm the SMM character of the systems, while CASSCF calculation along with simulation of the experimental data yields an antiferromagnetic interaction operating between the Dy3+ ions.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"44 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142867489","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0