Journal of Organometallic Chemistry最新文献

{"title":"Recent advances in palladium-catalyzed Suzuki-Miyaura cross-coupling reactions: Exploration of catalytic systems, reaction parameters, and ligand influences: A review","authors":"Dana A. Kader ,&nbsp;Mohammed Koksh Sidiq ,&nbsp;Salam Ghafour Taher ,&nbsp;Dara Muhammed Aziz","doi":"10.1016/j.jorganchem.2025.123569","DOIUrl":"10.1016/j.jorganchem.2025.123569","url":null,"abstract":"<div><div>The Suzuki-Miyaura cross-coupling reaction is a landmark in synthetic chemistry for its effective ability to form carbon-carbon bonds. This palladium-catalyzed reaction, which couples boronic acids with halides or pseudohalides, has drastically simplified the synthesis of complex organic compounds. It is already playing a major role in the production of pharmaceutical products as well as agricultural chemicals and biomaterials, thus significantly changing modern industry by promoting cleaner, more sustainable ways to operate chemical plants. In this paper, we provide a comprehensive overview of recent developments in palladium-catalyzed systems from 2020 to 2024, focusing on reaction parameters, and ligand variants, shedding light on their impact on yield, selectivity, kinetics, and purity. Our findings about the manifold potential of the Suzuki-Miyaura reaction to enhance reaction conditions and catalyst design underscore its flexibility. That makes possible a wide variety of uses.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1030 ","pages":"Article 123569"},"PeriodicalIF":2.1,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143444590","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":"Organometallic-based pyroptotic inducers for cancer immunotherapy","authors":"Jie Xu ,&nbsp;Ceyao Yang ,&nbsp;Qi Yu","doi":"10.1016/j.jorganchem.2025.123571","DOIUrl":"10.1016/j.jorganchem.2025.123571","url":null,"abstract":"<div><div>Cancer immunotherapy has been emerging as promising modality to treat malignant tumors, but the solid tumors with the “immune-cold” or immune-excluded nature induce the presence of the individual therapy discrepancy among patients. Pyroptosis, launched by gasdermin proteins, is favorable to trigger membrane perforation followed by the release of pro-inflammatory cytokines, which further induces antitumor immunity. Significantly, organometallic-based structures have been recently developed and exhibited the capacity of the pyroptotic activation through the acute redox homeostasis, which has been rising as an effective strategy for cancer immunotherapy. Up to date, few review has focused on this field. Therefore, this review provides a concentrated summary and discussion of the most recent works about organometallic-based pyroptotic activation. We hope that this review will be helpful to the readership who are interested in learning more about pyroptosis and the development of metal based pyroptotic inducers to efficiently augment the therapeutic efficacy.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1030 ","pages":"Article 123571"},"PeriodicalIF":2.1,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143444592","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":"Utilization of ruthenium(0) for σ-bond activation: Formation of organoruthenium complexes and emergence of their catalytic activity via in situ Ru-C bond cleavage","authors":"Mintu Das ,&nbsp;Aparajita Mukherjee ,&nbsp;Anannya Saha ,&nbsp;Samaresh Bhattacharya","doi":"10.1016/j.jorganchem.2025.123567","DOIUrl":"10.1016/j.jorganchem.2025.123567","url":null,"abstract":"<div><div>In this paper we report the successful utilization of ruthenium(0) for phenolic O<img>H followed by aryl C<img>H bond activations leading to the formation of ruthenium-hydrido and cycloruthenated complexes; and catalytic efficiency of these complexes towards transfer-hydrogenation (TH) of selected substrates. Reaction of [Ru⁰(CO)₃(PPh₃)₂] with 2-(arylazo)phenol (<strong>L-R</strong>; <em>R</em> = OCH₃, CH₃, H, Cl and NO₂) in refluxing toluene affords two products: a Ru-hydrido complex (depicted as <strong>1-R</strong>) formed via activation of the phenolic O<img>H bond; and a cycloruthenated complex (depicted as <strong>2-R</strong>) via successive phenolic O<img>H and aryl C<img>H bond activations. The formation mechanism of the two types of complexes was probed with DFT calculations, which revealed that initial phenolic O<img>H bond activation by Ru(0) center produces <strong>1-R</strong>. Then <strong>1-R</strong> converts, via absorption of thermal energy provided by the refluxing solvent, into its geometrical isomer with change in mutual disposition of the coordinated carbonyl and hydride. Finally, aryl C<img>H bond activation takes place, assisted by the coordinated hydride, to form the cycloruthenated complex <strong>2-R</strong> via elimination of molecular hydrogen. Exclusive formation of <strong>1-R</strong> or <strong>2-R</strong> complexes could also be achieved by carrying out the synthetic reaction respectively in refluxing acetone and <em>ortho</em>-xylene. Crystal structures of selected members from both the <strong>1-R</strong> and <strong>2-R</strong> families have been determined by X-ray diffraction method. The hydrido (<strong>1-R</strong>) complexes were found to efficiently catalyze TH of aryl/alkyl aldehydes and ketones to the corresponding alcohols, using 2-propanol as the provider of hydrogen. A solvent coordinated hydrido species (<strong>A</strong>), generated <em>in situ</em> via displacement of a PPh₃ from <strong>1-R</strong> by 2-propanol, is believed to function as the catalytically active species. The cycloruthenated (<strong>2-R</strong>) complexes, which do not contain any Ru-H moiety in them, are also found to catalyze similar TH with equal efficiency. Through electronic spectral studies it has been realized that the same catalytically active Ru-hydrido species (<strong>A</strong>) is generated <em>in situ</em> from the <strong>2-R</strong> complexes via 2-propanol assisted cleavage of the Ru-C bond.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1030 ","pages":"Article 123567"},"PeriodicalIF":2.1,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143463414","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":"Ni nanoparticle/Nitrogen-doped ordered mesoporous carbon as catalyst for C- and N-alkylation of ketones and amines with primary alcohols","authors":"Zahra Nasresfahani","doi":"10.1016/j.jorganchem.2025.123570","DOIUrl":"10.1016/j.jorganchem.2025.123570","url":null,"abstract":"<div><div>Nitrogen-doped mesoporous carbon containing Ni nanoparticles (Ni/N<img>OMC) were prepared and thoroughly characterized by Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray diffraction, transmission electron microscopy, scanning electron microscopy with energy dispersion X-ray spectroscopy, and N₂ adsorption-desorption analysis. The prepared Ni/N<img>OMC composite was a highly efficient catalyst for direct C- and N- alkylation of ketones and amines with alcohols under hydrogen-borrowing conditions. Based on this protocol, a broad range of ketones and amines could be efficiently alkylated with a set of primary alcohols to obtain their corresponding products in good to excellent isolated yields. Furthermore, this catalytic system could be applied to synthesize quinoline derivatives using 2-aminobenzyl alcohol as an alkylating agent. Satisfyingly, the Ni/N<img>OMC catalyst reused up to 6 runs without significant loss of activities.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1031 ","pages":"Article 123570"},"PeriodicalIF":2.1,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143548193","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":"Facile green synthesis of MoO2/BiOCl nanocomposite using Hibiscus rosa-sinensis leaf extract and its application in visible-light-driven oxidative transformations","authors":"Jayalakshmi M,&nbsp;Aatika Nizam","doi":"10.1016/j.jorganchem.2025.123566","DOIUrl":"10.1016/j.jorganchem.2025.123566","url":null,"abstract":"<div><div>This article describes a green approach for synthesizing MoO₂/BiOCl nanocomposite using a combustion procedure with <em>Hibiscus rosa-sinensis</em> leaf extract as a renewable fuel source, which also acts as a reducing and stabilizing agent. The synthesized material is characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and Fourier-transform infrared spectroscopy (FTIR), confirming the successful formation of the nanocomposite. The photocatalytic performance of MoO₂/BiOCl nanocomposite was evaluated for visible-light-driven oxidative transformations of different aromatic amines to nitroarenes. The unique structure of MoO₂/BiOCl provides better accessibility to the reactant molecules, facilitating faster and more efficient oxidation. The advantages of this oxidative process are high catalytic efficiency, mild reaction conditions, recyclability, environmental sustainability, and producing nitroarenes in good to exceptional yields (67–95 %). The conversion of the compounds was validated using gas chromatography-mass spectrometry (GC–MS), ¹H NMR, and ¹³C NMR. The results demonstrated that the MoO₂/BiOCl nanocomposite exhibited enhanced photocatalytic activity compared to its components, attributed to the synergistic effects between MoO₂ and BiOCl. The use of <em>Hibiscus rosa-sinensis</em> leaf extract in the synthesis is not only environmentally friendly and cost-effective but also contributes to the stability and efficiency of the nanocomposite.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1029 ","pages":"Article 123566"},"PeriodicalIF":2.1,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143421533","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":"APTES immobilized copper-doped nitrogen quantum dots (CuNPs@N-GQDs@APTES): An efficient heterogeneous nanocatalyst for multicomponent synthesis of 5-substituted-1H-tetrazoles","authors":"Kiran S. Bagade,&nbsp;Arjun S. Kumbhar","doi":"10.1016/j.jorganchem.2025.123565","DOIUrl":"10.1016/j.jorganchem.2025.123565","url":null,"abstract":"<div><div>A highly efficient and surface-bound aminated CuNPs@N-GQDs@APTES nanocatalyst has been synthesized and employed for the one-pot three-component reaction of various aromatic aldehydes, sodium azide, and hydroxylamine hydrochloride for the synthesis of 5-substituted 1<em>H</em>-tetrazoles. The characteristic properties of synthesized nanocatalysts were investigated using various characterization techniques. The catalyst was applied to synthesize structurally diverse 5-substituted 1<em>H</em>-tetrazoles with 85–96 % yield in 80–210 min under eco-friendly reaction conditions such as use of water at room temperature. Furthermore, the nanocatalyst was employed in four consecutive reactions cycles, with slight decrease in catalytic activity. The nanocatalyst exhibited remarkable advantageous characteristics, including high TON (19,559–23,471) and TOF (93–260 h^-1), ease of recovery, and efficient recyclability with minimal loss of catalytic activity.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1030 ","pages":"Article 123565"},"PeriodicalIF":2.1,"publicationDate":"2025-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143453616","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":"Green approach to Ullmann and Sonogashira cross-coupling reactions in water: Co-MOF as a robust and recyclable nanostructure","authors":"Norah Algethami ,&nbsp;Marwea Al-hedrewy ,&nbsp;Dharmesh Sur ,&nbsp;Suhas Ballal ,&nbsp;Manal Morad Karim ,&nbsp;Abhayveer Singh ,&nbsp;S. Sunitha ,&nbsp;Rajashree Panigrahi","doi":"10.1016/j.jorganchem.2025.123563","DOIUrl":"10.1016/j.jorganchem.2025.123563","url":null,"abstract":"<div><div>This work focuses on developing a novel metal-organic framework (MOF) and its application as a catalyst for carbon-oxygen and carbon-carbon bond formation. The catalytic transformation of aromatic halides is particularly challenging and holds significant importance in modern organic synthesis. Cross-coupling reactions that create carbon-heteroatom linkages are highly valued due to their widespread use in synthesizing of bioactive compounds and natural products. Consequently, the search for improved heterogeneous catalytic systems remains a key research priority. In this study, a cobalt-based MOF was synthesized using 4-amino-3-hydroxybenzoic acid, terephthalaldehyde, and cobalt acetate. This stable, efficient metal organic framework was characterized via FT-IR, TGA, CHNO, TEM, ICP, FE-SEM and BET techniques. Comprehensive characterization confirmed its structure and catalytic potential for cross-coupling reactions. The developed protocol offers an efficient and straightforward approach for C–O and C<img>C bond formation, delivering excellent product yields. This method was specifically applied to Ullmann and Sonogashira reactions, marking the first reported use of Co-MOF as nanostructure in such applications. The use of cobalt as a replacement for expensive palladium not only reduces costs but also significantly enhances the sustainability and accessibility of this process. Compared to existing methods, this strategy offers several advantages, including high efficiency, short reactions, catalyst stability, and minimal environmental impact. Additionally, the cobalt-MOF catalyst is easily recovered from reaction mixtures and retains its activity over multiple cycles, making it economical and environmentally friendly.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1029 ","pages":"Article 123563"},"PeriodicalIF":2.1,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143394555","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 and properties of diphenylphosphanyl and di-isopropylphosphanyl triphenylsilanes and pentaphenyldisilanes","authors":"Mike Friebel ,&nbsp;Uwe Böhme ,&nbsp;Edwin Kroke","doi":"10.1016/j.jorganchem.2025.123555","DOIUrl":"10.1016/j.jorganchem.2025.123555","url":null,"abstract":"<div><div>A new, less hazardous synthetic pathway to chloropentaphenyldisilane, ClSi₂Ph₅, has been developed. Starting from this compound and lithium diorganophosphides, the two previously unknown diorganophosphanyldisilanes (diphenylphosphanyl)pentaphenyldisilane, Ph₂PSi₂Ph₅, and (di-isopropylphosphanyl)pentaphenyldisilane, (<em>i</em>-Pr)₂PSi₂Ph₅, were prepared. To compare these compounds with the corresponding monosilanes, the known (diphenylphosphanyl)triphenylsilane, Ph₂PSiPh₃, and the unknown (di-isopropylphosphanyl)triphenylsilane, (<em>i</em>-Pr)₂PSiPh₃, were prepared, too. The former was prepared via new synthetic routes. The compounds were characterized with IR-, Raman-, ³¹P-, ²⁹Si-, and ¹H NMR spectroscopy and melting point determination. Single crystal structure analyses of ClSi₂Ph₅ and (<em>i</em>-Pr)₂PSiPh₃ were carried out and confirm the results presented.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1029 ","pages":"Article 123555"},"PeriodicalIF":2.1,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143388049","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":"Investigations into the reactivity of a molybdenocene formamidinate complex","authors":"Joscha Nellesen,&nbsp;Christian Ganter","doi":"10.1016/j.jorganchem.2025.123556","DOIUrl":"10.1016/j.jorganchem.2025.123556","url":null,"abstract":"<div><div>A cationic molybdenocene amidinate complex was investigated in view of its suitability to serve as a precursor for a metalla-N-heterocyclic carbene. Upon deprotonation, an amidinate complex with a cyclopenatdiene substituent at the amidinate C atom was identified. This points to the intermediate formation of the sought-after carbene which nucleophilicly attacks a Cp ring of the remaining cationic molybdenocene precursor and subsequent fragmentation. In contrast, the nucleophilic attack of standard imidazolylidenes to the cationic molybdenocene amidinate yields stable adducts with a η⁴-cyclopentadiene ligand. The rotational dynamics of this structure has been studied by variable temperature NMR studies. The experimental findings are supported by DFT calculations.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1029 ","pages":"Article 123556"},"PeriodicalIF":2.1,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143348749","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":"Synthesis of rhodium complexes with chiral diene ligands based on R-carvone","authors":"Tatiana N. Petrushina,&nbsp;Alexey N. Rodionov,&nbsp;Yulia V. Nelyubina,&nbsp;Dmitry S. Perekalin","doi":"10.1016/j.jorganchem.2025.123554","DOIUrl":"10.1016/j.jorganchem.2025.123554","url":null,"abstract":"<div><div>Allylic chlorination of <em>R</em>-carvone and subsequent nucleophilic substitution produced chiral diene ligands with additional pyrazole, phthalimide, or diethyl phosphonate coordinating groups. Reactions of these ligands with [(C₂H₄)₂RhCl]₂ produced the corresponding 16-electron rhodium complexes (carvone-L)RhCl. The pyrazole-based ligand formed the most stable complex, which was characterized by the X-ray diffraction. This complex catalyzed the insertion of aryldiazoacetates into <em>B</em>−<em>H</em> bond and cyclopropanation of 2,3-dihydrofurane but gave only racemic products.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1029 ","pages":"Article 123554"},"PeriodicalIF":2.1,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143268357","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}