Journal of Organometallic Chemistry最新文献

{"title":"Synthesis and protonation reactions of nitrosyl complexes [M2Cp(μ-κ:η5-C5H4)(μ-PR2)(CO)(NO)2] to give κ:η-NO-bridged derivatives (M = Mo, W; R = Cy, tBu)","authors":"Ana M. Guerra,&nbsp;Adrián Toyos,&nbsp;M. Angeles Alvarez,&nbsp;Daniel García-Vivó,&nbsp;Miguel A. Ruiz","doi":"10.1016/j.jorganchem.2024.123475","DOIUrl":"10.1016/j.jorganchem.2024.123475","url":null,"abstract":"<div><div>The title compounds were prepared upon reaction of BAr’₄⁻ salts of the known cations [M₂Cp₂(<em>μ</em>-PR₂)(CO)₂(NO)₂]⁺ (M = Mo, W; R = Cy, <em>^t</em>Bu; Ar’ = 3,5-C₆H₃(CF₃)₂), with commercial Me₃NO·2H₂O in fluorobenzene solution at 273 K, this promoting decarbonylation and cyclopentadienyl deprotonation to yield complexes with cyclopentadienylidene ligands bridging the metal centres (W−W = 2.9917(5) Å when R = Cy). The use of dichloromethane as solvent, however, triggered a competitive chloride abstraction reaction by the Mo compounds that yielded the chloride complexes [Mo₂Cp₂Cl(<em>μ</em>-PR₂)(CO)(NO)₂], specifically formed with an <em>anti</em> disposition of the Cp ligands relative to the Mo₂P plane, and <em>cis</em> positioning of carbonyl and chloride ligands relative to the P atom (Mo−Cl = 2.336(4) Å when R = <em>^t</em>Bu). Protonation of the cyclopentadienylidene-bridged complexes with [H(OEt₂)₂](BAr’₄) yielded the BAr’₄⁻ salts of the dicyclopentadienyl cations [M₂Cp₂(<em>μ</em>-<em>κ:η</em>-NO)(<em>μ</em>-PR₂)(CO)(NO)]⁺ (Mo−Mo = 3.1027(2) Å when R = <em>^t</em>Bu; W−W = 3.0446(7) Å when R = Cy), which display bridging nitrosyl ligands in the rare linear <em>end-on:side-on</em> coordination mode, and are kinetic rather than thermodynamic products, according to density functional theory calculations. When using HBF₄·OEt₂ as protonation reagent on the P<em>^t</em>Bu₂-bridged complexes, however, coordination of the external anion (in the <em>κ</em>¹-mode) also takes place, to yield the tetrafluoroborate complexes [M₂Cp₂(<em>κ</em>¹-BF₄)(<em>μ</em>-P<em>^t</em>Bu₂)(CO)(NO)₂] as unique (Mo) or major (W) products. Methylation of the same cyclopentadienylidene complexes with [Me₃O](BF₄) was only observed for the tungsten cation, and took place specifically at the O atom of one nitrosyl ligand to give [W₂Cp(<em>μ</em>-<em>κ:η</em>⁵-C₅H₄)(NOMe)(<em>μ</em>-P<em>^t</em>Bu₂)(CO)(NO)](BF₄), a complex displaying a linear methoxyimido ligand (W−N = 1.746(4) Å; W−N−O = 163.5(4)^o).</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1025 ","pages":"Article 123475"},"PeriodicalIF":2.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143138872","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The effective role of reusable Mn(III) Schiff‐base nano-catalyst in carrying out Chromene & Biginelli reactions under eco-friendly conditions","authors":"Mahboobeh-Sadat Mashhoori,&nbsp;Reza Sandaroos","doi":"10.1016/j.jorganchem.2024.123486","DOIUrl":"10.1016/j.jorganchem.2024.123486","url":null,"abstract":"<div><div>The development of efficient and recyclable catalysts is crucial for sustainable organic synthesis. A magnetic heterogeneous catalyst containing Mn(III) Schiff base covalently attached to Fe₃O₄@SiO₂ nanoparticles through imidazolium linker [Fe₃O₄@SiO₂-S-Im(Br)-SB-Mn(III)] was synthesized. The prepared nano-catalyst was characterized using various analytical methods (FT-IR, EDX, SEM, TEM, XRD, VSM, TGA, ICP-OES, and AAS). The efficiency of the nano-catalyst was investigated in the Chromene &amp; Biginelli reactions using a one-pot three-component synthesis of 2-amino-tetrahydro-4<em>H</em>-chromene-3-carbonitrile and 3,4-dihydropyrimidine-2(1<em>H</em>)-ones/thiones derivatives. The catalyst was found to be highly efficient in the synthesis of these derivatives in water and solvent-free conditions. The results demonstrated that the products were synthesized with excellent yields (98 %) within 5–10 min under very mild conditions. The nano-catalyst was re-used for eight consecutive cycles without any significant loss of catalytic activity.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1025 ","pages":"Article 123486"},"PeriodicalIF":2.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143138896","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rational design of chloride-based ionic iridium(III) complex to construct phosphorescent nanoparticles for cancer cell imaging","authors":"Xiaoli Li,&nbsp;Mengyao He,&nbsp;Rui Liu,&nbsp;Song Guo,&nbsp;Yuanli Liu","doi":"10.1016/j.jorganchem.2024.123485","DOIUrl":"10.1016/j.jorganchem.2024.123485","url":null,"abstract":"<div><div>In the process of cancer cell proliferation and metastasis, folate receptors (FRα, FRβ, and FRγ) play a facilitating role. More importantly, folate receptor, especially FRα, is expressed less in normal tissues but overexpressed in tumor tissues, making it a promising target for anticancer therapy. As a result, various probes targeting FRα have been developed for tumor detection. In this study, a new chloride-based ionic phosphorescent iridium(III) complex is rationally designed and synthesized, and then the phosphorescent nanoparticle (Ir NPs) is prepared by co-precipitation of iridium(III) complex with DSPE-PEG₂₀₀₀ and DSPE-PEG₂₀₀₀-FA, possessing the following advantages: good water solubility, exceptional biocompatibility, favorable surface properties, and excellent phosphorescence properties. Because of these advantages, Ir NPs are exceptionally suitable for biological application. Finally, cellular imaging, as a form of biological application, has been fully investigated. The results show that DSPE-PEG₂₀₀₀-FA can effectively recognize the over-expressed FRα on the surface of various cells, such as KB and MDA-MB-231 cells. We believe that the Ir NPs could be used as a promising phosphorescent probe for selective biological imaging.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1025 ","pages":"Article 123485"},"PeriodicalIF":2.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143138897","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Catalytic potential of fluorescein under visible light irradiation: Enabling single-pot open flask synthesis of novel pyrazolyl methanesulfonamides","authors":"Lokesh Kumar S ,&nbsp;Sankar Ganesh Ramaraj ,&nbsp;Sumaiya Tabassum ,&nbsp;Sony J. Chundattu ,&nbsp;Santhosh Govindaraju","doi":"10.1016/j.jorganchem.2024.123476","DOIUrl":"10.1016/j.jorganchem.2024.123476","url":null,"abstract":"<div><div>This groundbreaking study introduces a novel and efficient method for synthesizing a range of substituted pyrazolyl methanesulfonamides through a five-component cyclocondensation reaction. This reaction incorporates five different components, such as ethyl acetoacetate, hydrazine, dimedone, benzaldehydes, substituted phenyl acetonitriles, and methyl sulfonyl chloride was made to react under visible light irradiation, with fluorescein serving as an effective catalyst and ethanol as solvent for 30 mintues. This method offers significant advantages, including simplified handling, higher yields of target products with shorter reaction times, and easier purification processes. We successfully synthesized around 15 novel pyrazolyl methanesulfonamide derivatives with high efficiency. Comprehensive spectral characterization confirmed the structural integrity and purity of these derivatives, demonstrating the robustness and versatility of this approach. Facilitated by visible light and utilizing fluorescein as a bio-friendly catalyst, this methodology is both green and sustainable. This innovative approach not only streamlines the synthesis of pyrazolyl methanesulfonamides but also holds considerable promise for advancing research and applications in fields such as medicinal chemistry and materials science.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1025 ","pages":"Article 123476"},"PeriodicalIF":2.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143138857","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A novel and green approach for the synthesis of copper nanoparticles and their applications in reduction of nitroarenes and degradation of organic dyes","authors":"Babak Kaboudin ,&nbsp;Bahman Burunli ,&nbsp;Mahdi Nazerian ,&nbsp;Tianjian Zhang ,&nbsp;Yanlong Gu","doi":"10.1016/j.jorganchem.2024.123477","DOIUrl":"10.1016/j.jorganchem.2024.123477","url":null,"abstract":"<div><div>Copper nanoparticles (Cu-NPs) were synthesized using a complex of copper with β-cyclodextrin (Cu₂-<em>β</em>-CD) by the hydrothermal method in an aqueous solution. The synthesis proceeded without adding any additives such as reducing agents. The structural characterization of copper nanoparticles has been carried out by scanning electron microscopy (SEM) images, EDS, XRD, and TGA analysis. Application of the catalytic activity of the obtained Cu-NPs was performed for the reduction of nitroaromatic compounds. A catalytic degradation of Methylene Blue and Methyl Orange solutions in the presence of Cu-NPs was also studied in order to examine the nanoparticles influence on degradation.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1025 ","pages":"Article 123477"},"PeriodicalIF":2.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143138865","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A novel reusable polymer supported palladium catalyst for Heck reaction","authors":"Pambingal Rajan Sruthi ,&nbsp;Sivan Malini ,&nbsp;Sasi Silpa ,&nbsp;Saithalavi Anas","doi":"10.1016/j.jorganchem.2024.123452","DOIUrl":"10.1016/j.jorganchem.2024.123452","url":null,"abstract":"<div><div>With the rapid development of “green” chemistry; researchers are highly interested towards more sustainable approaches and prefer to choose eco-friendly synthetic routes and materials. This paper deals with the development of a novel reusable heterogeneous palladium catalyst for Heck reaction. The catalyst (<strong>mPAN-Pd</strong>) was developed by a simple procedure <em>via</em> synthetic modification of polyacrylonitrile (PAN) with monoethanolamine (MEA) followed by complexation with palladium chloride (PdCl₂). After detailed characteristic studies, the catalytic efficiency of <strong>mPAN-Pd</strong> in Heck coupling reaction was systematically evaluated and optimised the reaction condition through a set of experiments. This heterogeneous catalytic system was found be applicable over a series of aryl halides and terminal alkenes leading to corresponding coupling products in good yields. Furthermore, this catalyst offers easy recyclability by simple filtration and reused for at least 5 cycles of Heck reaction without losing much of its activity.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1025 ","pages":"Article 123452"},"PeriodicalIF":2.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143138867","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis, structures and photocatalytic properties of two binuclear sulfur-bridged cymene-ruthenium fluorodithiophosphates","authors":"Song Pan,&nbsp;Chong Chen,&nbsp;Qing-Wen Liang,&nbsp;Ai-Quan Jia,&nbsp;Qian-Feng Zhang","doi":"10.1016/j.jorganchem.2024.123481","DOIUrl":"10.1016/j.jorganchem.2024.123481","url":null,"abstract":"<div><div>A binuclear complex [(<em>η⁶</em>-<em>p</em>-cymene)₂Ru₂Cl₂(S₂POF)] (<strong>1</strong>) was generated by combining a binuclear ruthenium precursor [(<em>η⁶</em>-<em>p</em>-cymene)RuCl₂]₂ with an equivalent amount of [NⁿPr₄]₂[S₅P₂F₂] in dichloromethane at room temperature. Treatment of [(<em>η⁶</em>-<em>p</em>-cymene)RuCl₂]₂ with two equivalents of [NⁿPr₄]₂[S₅P₂F₂] in dichloromethane at reflux in the presence of AgNO₃ led to isolation of a binuclear ruthenium complex [(<em>η⁶</em>-<em>p</em>-cymene)Ru(S₂POF)]₂ (<strong>2</strong>). Complexes <strong>1</strong> and <strong>2</strong> were characterized by IR, <em>multi</em>-NMR (¹H, ³¹P, ¹⁹F) and UV–vis spectroscopies. The structures of complexes <strong>1</strong> and <strong>2</strong> have been established by single-crystal X-ray crystallography. In addition, the photocatalytic properties of complex <strong>2</strong> for hydrogen production from water splitting under visible light were also investigated.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1025 ","pages":"Article 123481"},"PeriodicalIF":2.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143139405","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Preparation and characterization of nickel hybrid material and its catalytic activity","authors":"R. Bagtache ,&nbsp;M. Trari","doi":"10.1016/j.jorganchem.2025.123552","DOIUrl":"10.1016/j.jorganchem.2025.123552","url":null,"abstract":"<div><div>An organic-inorganic hybrid metal phosphate was synthetized by hydrothermal route at 180 °C. It was characterized by X-ray diffraction (XRD), thermal and chemical analysis, FTIR and NMR spectroscopies, Electron Spin Resonance (ESR), SEM analysis and UV–Visible diffuse reflectance. These analyses allowed us to propose the formula Na[PW₆Ni₃O₂₇][C₂N₂H₁₀]_0.5[C₂N₂H₉]₃·3H₂O (Ni-Ethylene Diamine) and thermal gravimetry shows stability up to 350 °C. Increasing conductivity with temperature indicates a semiconducting behavior with a room temperature conductivity σ₃₀₀ _K of 1.2 × 10^–4 (Ω-cm)^-1. The paramagnetic ion Ni(II) (3<em>d⁷</em>), produces a disturbance in the NMR spectra. The FT-IR spectrum shows peaks at 500 and 730 cm^-1, attributed respectively to Ni-O and W-O bonds while the characteristic peak of PO₄ is observed at 1030 cm^-1. SEM micrograph shows crystals in the form of hexagonal needles with more or less homogeneous shapes (∼ 15 µm) and an average porosity. The UV–Visible spectrum of the hybrid compound shows two bands at 250 and 320 nm, attributed to ligand-metal charge transfer (O^2-: <em>2p</em> → Ni²⁺: <em>4</em> <em>s</em>). The indirect allowed transition (2.30 eV) is assigned to the internal transition of Ni²⁺ (<em>e → t₂</em>). The ESR spectrum indicates a <em>g</em>-factor of 2.005, a signature of Ni²⁺ tetrahedrally bonded to O₂^- ions. The compound was successfully tested in the oxidation of acetaldehyde (CH₃CHO) to acetic acid (CH₃COOH). This study was conducted by varying two parameters namely the temperature (40, 50 and 60 °C) and the nature of the oxidant: H₂O₂ and tert‑butyl hydroxide peroxide. The best result is obtained with H₂O₂ at 60 °C, with an activity twice as high as without catalyst.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1029 ","pages":"Article 123552"},"PeriodicalIF":2.1,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143351476","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ruthenium(II)-Catalyzed Synthesis of N-Heterocycles via Acceptorless Dehydrogenative Condensation","authors":"Chong Zhang ,&nbsp;Bowen Hu ,&nbsp;Dafa Chen ,&nbsp;Wangsheng Liu ,&nbsp;Hao Guo","doi":"10.1016/j.jorganchem.2025.123545","DOIUrl":"10.1016/j.jorganchem.2025.123545","url":null,"abstract":"<div><div>Four bidentate ruthenium(II) complexes <strong>1–4</strong> were tested as catalysts for the synthesis of quinolines via acceptorless dehydrogenative condensation (ADC) strategy, using <em>o</em>-aminobenzyl alcohol and ketones as the starting materials, and complex <strong>4</strong> exhibited the highest activity. With 0.3 mol% catalyst loading and 1.0 equivalent of KOH, 26 quinoline derivatives were isolated in high yields within 2 hours at 120 °C. Moreover, under similar conditions, this multifunctional catalyst is also applicable for the preparation of other N-heterocycles, and a series of naphthyridines, pyridines and pyrroles were generated.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1029 ","pages":"Article 123545"},"PeriodicalIF":2.1,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143348750","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesize and characterization of Fe2O3 nanoparticles and its potential as a photocatalyst","authors":"Hadil Jubair Mayouf ,&nbsp;Mohammed Faiad Naief ,&nbsp;Samar Naser Mohammed ,&nbsp;Ahmed Mishaal Mohammed","doi":"10.1016/j.jorganchem.2025.123543","DOIUrl":"10.1016/j.jorganchem.2025.123543","url":null,"abstract":"<div><div>Methylene blue (MB) is used extensively in medicine; nevertheless, excessive dosages (≥7 mg/kg) of MB can oxidize hemoglobin directly, resulting in methemoglobinemia. Especially in newborns, hemolysis is linked to doses of &gt;15 mg/kg. It may also impede the clinical manifestations of cyanosis and discolor mucosal membranes and secretions. In this work, iron oxide nanoparticles (Fe₂O₃NPs) were synthesized utilizing green chemistry methods using fresh leaves of red cabbage (Brassica oleracea L. var. capitata f, rubra) extract and calcined at 700 °C temperatures to get the hematite phases. In this approach, biomolecules such as alkaloids, steroids, flavonoids, terpenoids, phenolic, flavonoids, anthocyanins, and glucosinolates presence in the red cabbage extract have been shown to work as encapsulating agents for Fe₂O₃NPs. The various physical and chemical characteristics of synthesized Fe₂O₃NPs with spherical solid shapes and having a diameter ranging from 29.03 to 49.13 nm were characterized using FESEM, TEM, XRD, FTIR, and UV–visible spectroscopy techniques. The photocatalytic activity of synthesized Fe₂O₃NPs was tested against methylene blue (MB) under UV-visible light. The photocatalyst degraded approximately 65.5 % of the original MB dye at a rate of 0.0043 min⁻¹ during 240 min of irradiation.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1029 ","pages":"Article 123543"},"PeriodicalIF":2.1,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143267981","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}