Pub Date : 2025-12-11DOI: 10.1016/j.jorganchem.2025.123978
Suku Arya , Fathimathul Rinsana , Shajahan Rubina , Saithalavi Anas
Chan-Lam coupling is an efficient transition metal catalyzed CN bond formation strategy towards the synthesis of various N-arylated molecular structures. Despite remarkable advancement in the field, the construction of CN remains challenging due to harsh reaction conditions and the use of expensive catalysts. Here, we have developed a facile and reusable polymer supported copper catalyst (mPANCu) for Chan-Lam coupling reaction by incorporating copper (II) chloride into suitably functionalized polyacrylonitrile (PAN). After detailed characterization (FTIR, XRD, XPS, ICPMS and EDAX analyses), mPANCu was successfully optimized as an efficient heterogeneous catalyst for Chan-Lam coupling reaction between p-anisidine (1a) and phenylboronic acid (2a) under milder reaction conditions. The generality of this reaction was further established by using a series of substituted anilines and aryl boronic acids in presence of Na2CO3 in methanol under room temperature conditions. Moreover, this catalyst offers excellent recyclability by simple filtration and reused for successive reaction cycles without much appreciable loss in its stability and activity.
{"title":"A facile and reusable heterogeneous catalyst for chan- lam coupling reaction","authors":"Suku Arya , Fathimathul Rinsana , Shajahan Rubina , Saithalavi Anas","doi":"10.1016/j.jorganchem.2025.123978","DOIUrl":"10.1016/j.jorganchem.2025.123978","url":null,"abstract":"<div><div>Chan-Lam coupling is an efficient transition metal catalyzed C<img>N bond formation strategy towards the synthesis of various N-arylated molecular structures. Despite remarkable advancement in the field, the construction of C<img>N remains challenging due to harsh reaction conditions and the use of expensive catalysts. Here, we have developed a facile and reusable polymer supported copper catalyst (<strong>mPAN<img>Cu</strong>) for Chan-Lam coupling reaction by incorporating copper (II) chloride into suitably functionalized polyacrylonitrile (PAN). After detailed characterization (FTIR, XRD, XPS, ICPMS and EDAX analyses), <strong>mPAN<img>Cu</strong> was successfully optimized as an efficient heterogeneous catalyst for Chan-Lam coupling reaction between <em>p-</em>anisidine (<strong>1a</strong>) and phenylboronic acid (<strong>2a</strong>) under milder reaction conditions. The generality of this reaction was further established by using a series of substituted anilines and aryl boronic acids in presence of Na<sub>2</sub>CO<sub>3</sub> in methanol under room temperature conditions. Moreover, this catalyst offers excellent recyclability by simple filtration and reused for successive reaction cycles without much appreciable loss in its stability and activity.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1045 ","pages":"Article 123978"},"PeriodicalIF":2.1,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797750","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}
Ru(II)–arene organometallic complexes are genuine species that provide a tunable platform for anticancer therapy, rivaling platinum-based drugs through ligand design versatility and diverse mechanisms. In contrast, clinically relevant non-arene Ru(III) coordination compounds such as NAMI-A and BOLD-100 lack direct Ru–C bonds, but are included in this review for their complementary mechanistic and translational relevance. This review integrates recent synthetic advancements, including microwave-assisted synthesis and ligand exchange strategies, with mechanistic insights driving their antitumor, anti-angiogenic, and anti-metastatic effects. Key pathways include reactive oxygen species (ROS) generation, endoplasmic reticulum (ER) stress via GRP78 modulation, and selective inhibition of redox enzymes like thioredoxin reductase (TrxR) and cathepsin B. Clinically relevant Ru-based drug candidates include the non-arene Ru(III) coordination compounds NAMI-A ([ImH][trans-RuCl₄(DMSO)(Im)], where Im = imidazole) and BOLD-100 ([Na][trans-RuCl₄(Ind)₂]), as well as the organometallic Ru(II)–arene complex RAPTA-C ([Ru(η⁶-p-cymene)(PTA)Cl₂], where PTA = 1,3,5-triaza-7-phosphaadamantane). Among these, only RAPTA-C represents a true piano-stool organometallic complex, whereas NAMI-A and BOLD-100 exemplify Ru(III) coordination (non-arene) species. NAMI-A has shown antimetastatic activity in lung cancer models, BOLD-100 has progressed to phase Ib/IIa trials in gastrointestinal cancers, and RAPTA-C demonstrates anti-invasive efficacy in preclinical studies. Structure–activity relationships (SAR) reveal that arene and auxiliary ligands, such as p-cymene or PTA, modulate lipophilicity, cellular uptake, and tumor selectivity, while Ru(II)/Ru(III) oxidation states govern activation in hypoxic microenvironments. Their inherent polypharmacological profile and multisite binding to diverse biomolecules necessitate a holistic, speciation-aware interpretation of biodistribution and off-target effects. Despite progress, challenges like hydrolytic instability, variable speciation, poor penetration into dense tumors, and regulatory hurdles persist. We propose a roadmap integrating speciation-aware bioassays, DFT/machine learning-driven SAR, biomarker-guided trials, and theranostic formulations with radiolabels (e.g., Ru-97/103) to enhance stability, selectivity, and clinical translation. By distinguishing between Ru(II)–arene organometallic scaffolds and Ru(III) non-arene clinical leads, this review unites synthetic precision with multimodal mechanisms, highlighting the collective potential of ruthenium-based agents to advance precision oncology with lower toxicity and improved efficacy against resistant cancers.
{"title":"Ruthenium-based anticancer agents: Focus on mononuclear Ru(II)–arene organometallic scaffolds and Ru(III) non-arene coordination compounds as clinical leads","authors":"Narinderjit Singh Sawaran Singh , Luma Hussain Saleh , G. PadmaPriya , Subhashree Ray , Amrita Pal , Vimal Arora , Khalmurat Iliev , Zukhra Atamuratova , Davronbek Yulchiev , Aseel Smerat , Shahad Muthana Qasim","doi":"10.1016/j.jorganchem.2025.123981","DOIUrl":"10.1016/j.jorganchem.2025.123981","url":null,"abstract":"<div><div>Ru(II)–arene organometallic complexes are genuine species that provide a tunable platform for anticancer therapy, rivaling platinum-based drugs through ligand design versatility and diverse mechanisms. In contrast, clinically relevant non-arene Ru(III) coordination compounds such as NAMI-A and BOLD-100 lack direct Ru–C bonds, but are included in this review for their complementary mechanistic and translational relevance. This review integrates recent synthetic advancements, including microwave-assisted synthesis and ligand exchange strategies, with mechanistic insights driving their antitumor, anti-angiogenic, and anti-metastatic effects. Key pathways include reactive oxygen species (ROS) generation, endoplasmic reticulum (ER) stress via GRP78 modulation, and selective inhibition of redox enzymes like thioredoxin reductase (TrxR) and cathepsin B. Clinically relevant Ru-based drug candidates include the non-arene Ru(III) coordination compounds NAMI-A ([ImH][trans-RuCl₄(DMSO)(Im)], where Im = imidazole) and BOLD-100 ([Na][trans-RuCl₄(Ind)₂]), as well as the organometallic Ru(II)–arene complex RAPTA-C ([Ru(η⁶-p-cymene)(PTA)Cl₂], where PTA = 1,3,5-triaza-7-phosphaadamantane). Among these, only RAPTA-C represents a true piano-stool organometallic complex, whereas NAMI-A and BOLD-100 exemplify Ru(III) coordination (non-arene) species. NAMI-A has shown antimetastatic activity in lung cancer models, BOLD-100 has progressed to phase Ib/IIa trials in gastrointestinal cancers, and RAPTA-C demonstrates anti-invasive efficacy in preclinical studies. Structure–activity relationships (SAR) reveal that arene and auxiliary ligands, such as p-cymene or PTA, modulate lipophilicity, cellular uptake, and tumor selectivity, while Ru(II)/Ru(III) oxidation states govern activation in hypoxic microenvironments. Their inherent polypharmacological profile and multisite binding to diverse biomolecules necessitate a holistic, speciation-aware interpretation of biodistribution and off-target effects. Despite progress, challenges like hydrolytic instability, variable speciation, poor penetration into dense tumors, and regulatory hurdles persist. We propose a roadmap integrating speciation-aware bioassays, DFT/machine learning-driven SAR, biomarker-guided trials, and theranostic formulations with radiolabels (e.g., Ru-97/103) to enhance stability, selectivity, and clinical translation. By distinguishing between Ru(II)–arene organometallic scaffolds and Ru(III) non-arene clinical leads, this review unites synthetic precision with multimodal mechanisms, highlighting the collective potential of ruthenium-based agents to advance precision oncology with lower toxicity and improved efficacy against resistant cancers.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1045 ","pages":"Article 123981"},"PeriodicalIF":2.1,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797747","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}
Pub Date : 2025-12-10DOI: 10.1016/j.jorganchem.2025.123980
Meng Hu, Hai-Juan Shuai, Xiao-Meng Jin, Chen Gao, Chuan-Ming Jin
This work presents the synthesis of four bi-nuclear Ag(I)-NHC metallomacrocyclic assemblies Ag-NHC-1, 2, 3, and 4, through silver oxide reacted with the corresponding bi-NHC precursors NHC-1, 2, 3, and 4 based on imidazole and triazole rings, and an isomerization process from Ag-NHC-4 to the bi-nuclear Ag(I)-NHC metallomacrocyclic polymer Ag-NHC-P4. They were characterized by 1H NMR, 13C NMR, ESI–MS, and single-crystal X-ray diffraction (SCXRD) analysis. X-ray crystallography revealed that Ag-NHC-1, 2, 3, and 4 are box-type, U-shape and square-type bi-nuclear Ag(I)-NHC [2M+2L] metallomacrocyclic supramolecular assemblies with intramolecular Ag-π interactions, intramolecular and intermolecular π–π stacking interactions, whereas Ag-NHC-P4 functioned as an infinite 1D linearly arranged polymer containing two distinct square-type bi-nuclear Ag(I)-NHC metallomacrocyclic units. The in vitro cytotoxic activity observed in Ag-NHC-1, 2, 3, and 4 against lung cancer cells H157 indicates that they had significant inhibitory effects on lung cancer cells growth with a half maximal inhibitory concentration (IC50) value at 1.55, 0.25, 0.08 and 1.74 μM in H157 cells, respectively. The in vitro cytotoxicity order is Ag-NHC-3 > Ag-NHC-2 > Ag-NHC-1 > Ag-NHC-4, revealed this possibility to improve the anti-cancer activity of Ag(I)-NHC complexes through inducing N-heterocyclic carbene based on triazole rings and functional quinoline groups, owing to the naked N atoms of triazole and quinoline rings may be tuning the geometric structure of bi-nuclear Ag(I)-NHC assemblies and their biological compatibility.
{"title":"Four bi-nuclear Ag(I)-N-heterocyclic carbene metallomacrocyclic assemblies: Crystal structure, anti-lung cancer activity and isomerization to 1D Ag(I)-NHC polymer","authors":"Meng Hu, Hai-Juan Shuai, Xiao-Meng Jin, Chen Gao, Chuan-Ming Jin","doi":"10.1016/j.jorganchem.2025.123980","DOIUrl":"10.1016/j.jorganchem.2025.123980","url":null,"abstract":"<div><div>This work presents the synthesis of four bi-nuclear Ag(I)-NHC metallomacrocyclic assemblies Ag-NHC-1, 2, 3, and 4, through silver oxide reacted with the corresponding bi-NHC precursors NHC-1, 2, 3, and 4 based on imidazole and triazole rings, and an isomerization process from Ag-NHC-4 to the bi-nuclear Ag(I)-NHC metallomacrocyclic polymer Ag-NHC-P4. They were characterized by <sup>1</sup>H NMR, <sup>13</sup>C NMR, ESI–MS, and single-crystal X-ray diffraction (SCXRD) analysis. X-ray crystallography revealed that Ag-NHC-1, 2, 3, and 4 are box-type, U-shape and square-type bi-nuclear Ag(I)-NHC [2M+2L] metallomacrocyclic supramolecular assemblies with intramolecular Ag-π interactions, intramolecular and intermolecular π–π stacking interactions, whereas Ag-NHC-P4 functioned as an infinite 1D linearly arranged polymer containing two distinct square-type bi-nuclear Ag(I)-NHC metallomacrocyclic units. The in vitro cytotoxic activity observed in Ag-NHC-1, 2, 3, and 4 against lung cancer cells H157 indicates that they had significant inhibitory effects on lung cancer cells growth with a half maximal inhibitory concentration (IC<sub>50</sub>) value at 1.55, 0.25, 0.08 and 1.74 μM in H157 cells, respectively. The in vitro cytotoxicity order is Ag-NHC-3 > Ag-NHC-2 > Ag-NHC-1 > Ag-NHC-4, revealed this possibility to improve the anti-cancer activity of Ag(I)-NHC complexes through inducing N-heterocyclic carbene based on triazole rings and functional quinoline groups, owing to the naked N atoms of triazole and quinoline rings may be tuning the geometric structure of bi-nuclear Ag(I)-NHC assemblies and their biological compatibility.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1045 ","pages":"Article 123980"},"PeriodicalIF":2.1,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748498","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}
Herein, we report the synthesis and assessment of a new biogenic nanocomposite with silver nanoparticles based on a core-shell structure created by functionalising phytochemicals found in Nigella Sativa flower extract. UV-Vis spectroscopy, XRD, TEM, EDX, ICP-OES, and FE-SEM methods were used to evaluate the resultant nanocatalyst (Ag NPs/N. Sativa). Based on TEM images, the Ag NPs were spherical, monodispersed, and about 25–30 nm in size. Following a C-H activation method, the material's catalytic performance was evaluated in the high-yield synthesis of many propargylamine derivatives employing A3 coupling processes. The performance of the catalyst did not significantly decline even after seven consecutive uses. There were forty-five Wister rats used in the medical segment. These groups included two that received pretreatment with Ag NPs at varying dosages for 14 days, a normal group, and a group that received just isoproterenol treatment to induce myocardial infarction. Isoproterenol was subsequently administered to these pretreated groups. In addition to other downstream apoptotic and inflammatory mediators, the PI3K/Akt/mTOR expression was monitored. ECG, cardiac indicators, Nrf2, Keap1 expression, and other downstream antioxidant enzymes were also evaluated. Ag NPs treatment improved myocardial autophagy, inflammation, and apoptosis. It also controlled the PI3K/Akt/mTOR pathway, activated the Keap1/Nrf2/HO-1 pathway, and enhanced the effectiveness of antioxidant enzymes. By inhibiting the Keap1/Nrf2 pathway, SOD, GSH, GPx, GST, TNF-α, IL-6, IL-1β, NF-κB, Bcl2, Bax, caspase-3, caspase-9, and PI3K/Akt/mTOR pathway, the findings imply that Ag NPs may have a cardioprotective efficacy on myocardial infarction. Additionally, the therapy reduced the cardiac markers levels, lowered the infarct zone size, and lessened immune cell infiltration and myocardial necrosis.
{"title":"Cardioprotective effect of Ag nanoparticles green-formulated by Nigella Sativa on isoproterenol-induced cardiotoxicity following the PI3K/Akt/mTOR and Keap1/Nrf2/HO-1 pathways and its catalytic application for A3 coupling reaction","authors":"Yuan Yuan , Junwen Zhang , Narinderjit Singh Sawaran Singh , Dilbar Urazbaeva , Yodgor Kenjayev , Mashkhura Sultonova","doi":"10.1016/j.jorganchem.2025.123979","DOIUrl":"10.1016/j.jorganchem.2025.123979","url":null,"abstract":"<div><div>Herein, we report the synthesis and assessment of a new biogenic nanocomposite with silver nanoparticles based on a core-shell structure created by functionalising phytochemicals found in Nigella Sativa flower extract. UV-Vis spectroscopy, XRD, TEM, EDX, ICP-OES, and FE-SEM methods were used to evaluate the resultant nanocatalyst (Ag NPs/<em>N. Sativa</em>). Based on TEM images, the Ag NPs were spherical, monodispersed, and about 25–30 nm in size. Following a C-H activation method, the material's catalytic performance was evaluated in the high-yield synthesis of many propargylamine derivatives employing A<sup>3</sup> coupling processes. The performance of the catalyst did not significantly decline even after seven consecutive uses. There were forty-five Wister rats used in the medical segment. These groups included two that received pretreatment with Ag NPs at varying dosages for 14 days, a normal group, and a group that received just isoproterenol treatment to induce myocardial infarction. Isoproterenol was subsequently administered to these pretreated groups. In addition to other downstream apoptotic and inflammatory mediators, the PI3K/Akt/mTOR expression was monitored. ECG, cardiac indicators, Nrf2, Keap1 expression, and other downstream antioxidant enzymes were also evaluated. Ag NPs treatment improved myocardial autophagy, inflammation, and apoptosis. It also controlled the PI3K/Akt/mTOR pathway, activated the Keap1/Nrf2/HO-1 pathway, and enhanced the effectiveness of antioxidant enzymes. By inhibiting the Keap1/Nrf2 pathway, SOD, GSH, GPx, GST, TNF-α, IL-6, IL-1β, NF-κB, Bcl2, Bax, caspase-3, caspase-9, and PI3K/Akt/mTOR pathway, the findings imply that Ag NPs may have a cardioprotective efficacy on myocardial infarction. Additionally, the therapy reduced the cardiac markers levels, lowered the infarct zone size, and lessened immune cell infiltration and myocardial necrosis.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1045 ","pages":"Article 123979"},"PeriodicalIF":2.1,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748493","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}
Semiconductor quantum dots (QDs), exhibiting tunable size-dependent optical and electronic characteristics, have become revolutionary materials in different fields of science. This review is particularly devoted to their utilization in carbon conversion, which is an essential area to address climate change and reach net-zero emissions. High surface area, tunability of the band gap and excellent photochemical stability of QDs make them quite suitable for CO2 adsorption and reduction. In the review, various QD synthesis methods such as chemical vapor deposition, sol-gel method, hydrothermal method, and other methods are discussed that offer the possibility to regulate their size and characteristics. It also explores their incorporation with other hybrid systems such as metal organic frameworks and graphene to improve the carbon conversion performance. In addition, application of QDs in photocatalytic reduction of CO2 is also presented, as they show great promise in the conversion of CO2 to advantageous fuels and chemicals. Issues like scalability of the system, environmental issues and sustainability of the solution are also discussed. This systematic review summarizes future research and emphasizes the potential of QDs to transform carbon to attain the global carbon neutrality.
{"title":"State-of-art of quantum dots: A comprehensive review on photocatalytic carbon conversion","authors":"Sonia , Youssef Trabelsi , Ajay Kumari , M. Manjula , Sonam Goyal , Ashok Kumar , Lakshita Phor , Nidhi Rathee , Surjeet Chahal","doi":"10.1016/j.jorganchem.2025.123977","DOIUrl":"10.1016/j.jorganchem.2025.123977","url":null,"abstract":"<div><div>Semiconductor quantum dots (QDs), exhibiting tunable size-dependent optical and electronic characteristics, have become revolutionary materials in different fields of science. This review is particularly devoted to their utilization in carbon conversion, which is an essential area to address climate change and reach net-zero emissions. High surface area, tunability of the band gap and excellent photochemical stability of QDs make them quite suitable for CO<sub>2</sub> adsorption and reduction. In the review, various QD synthesis methods such as chemical vapor deposition, sol-gel method, hydrothermal method, and other methods are discussed that offer the possibility to regulate their size and characteristics. It also explores their incorporation with other hybrid systems such as metal organic frameworks and graphene to improve the carbon conversion performance. In addition, application of QDs in photocatalytic reduction of CO<sub>2</sub> is also presented, as they show great promise in the conversion of CO<sub>2</sub> to advantageous fuels and chemicals. Issues like scalability of the system, environmental issues and sustainability of the solution are also discussed. This systematic review summarizes future research and emphasizes the potential of QDs to transform carbon to attain the global carbon neutrality.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1045 ","pages":"Article 123977"},"PeriodicalIF":2.1,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797795","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}
Pub Date : 2025-12-06DOI: 10.1016/j.jorganchem.2025.123976
Pacifique Muhoza , Yu Sun , Harald Kelm , Subham Burai , Maximilian Luczak , Katharina Rediger , Philipp Weber , Mahir Sönmez , Ann-Katrin Britzius , Maria Wächtler , Gereon Niedner-Schatteburg , Marc H. Prosenc , Werner R. Thiel
In this study we describe the synthesis and characterization of iridium(III) complexes coordinated with bidentate 2-(amino)-4-(2-pyridinyl)pyrimidine ligands. Starting from [Ir(ppy)2(μ-Cl)]2 (ppy = 2-phenylpyridine), these ligands coordinate to the metal center via their N,N'-binding pocket leading to cationic iridium(III) complexes. In contrast, starting with [Ir(ppy)2(μ-OH)]2, provides threefold cyclometalated complexes. The photophysical properties of both types of iridium(III) complexes have been studied in detail. Furthermore, [Ir(ppy)2(μ-OH)]2 is a highly active catalyst for the transfer hydrogenation of ketones with 2-propanol as hydrogen source, operating without the addition of a base. To achieve comparable catalytic activity with [Ir(ppy)2(μ-Cl)]2, a 20-fold excess of KOH (relative to the amount of catalyst) must be used.
{"title":"Cyclometalated iridium complexes: Synthesis, photoluminescence, and catalysis","authors":"Pacifique Muhoza , Yu Sun , Harald Kelm , Subham Burai , Maximilian Luczak , Katharina Rediger , Philipp Weber , Mahir Sönmez , Ann-Katrin Britzius , Maria Wächtler , Gereon Niedner-Schatteburg , Marc H. Prosenc , Werner R. Thiel","doi":"10.1016/j.jorganchem.2025.123976","DOIUrl":"10.1016/j.jorganchem.2025.123976","url":null,"abstract":"<div><div>In this study we describe the synthesis and characterization of iridium(III) complexes coordinated with bidentate 2-(amino)-4-(2-pyridinyl)pyrimidine ligands. Starting from [Ir(ppy)<sub>2</sub>(μ-Cl)]<sub>2</sub> (ppy = 2-phenylpyridine), these ligands coordinate to the metal center via their <em>N,N</em>'-binding pocket leading to cationic iridium(III) complexes. In contrast, starting with [Ir(ppy)<sub>2</sub>(μ-OH)]<sub>2</sub>, provides threefold cyclometalated complexes. The photophysical properties of both types of iridium(III) complexes have been studied in detail. Furthermore, [Ir(ppy)<sub>2</sub>(μ-OH)]<sub>2</sub> is a highly active catalyst for the transfer hydrogenation of ketones with 2-propanol as hydrogen source, operating without the addition of a base. To achieve comparable catalytic activity with [Ir(ppy)<sub>2</sub>(μ-Cl)]<sub>2</sub>, a 20-fold excess of KOH (relative to the amount of catalyst) must be used.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1045 ","pages":"Article 123976"},"PeriodicalIF":2.1,"publicationDate":"2025-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797749","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}
A series of palladium N-heterocyclic carbene (NHC) complexes including trans-[Pd(NHC)Br2L] (L = C5H5N, 3-ClC5H4N, and N-methylimidazole) and [Pd(NHC)2Br2] have been prepared from {1-(benzyl)-3- (3,5-(bis(trifluoromethyl)benzyl)benzimidazolium bromide}. The structures of these new compounds were confirmed by NMR, FT-IR, and elemental analyses. The crystal structures of the dibromo- [1-(benzyl)-3- (3,5-(bis(trifluoromethyl)benzyl)benzimidazole-2-ylidene]-(pyridine)-palladium(II) and dibromo- [1-(benzyl)-3- (3,5-(bis(trifluoromethyl)benzyl)benzimidazole-2-ylidene]-(N-methylimidazole)-palladium(II) were determined by single-crystal X-ray diffraction. Palladium complexes were developed as efficient pre-catalysts for direct C4-arylation of 3,5-dimethylisoxazole and aryl bromides. Biological efficiency of trans-[Pd(NHC)Br2L]was evaluated by antioxidant activities like ABTS, OH and DPPH radical scavenging activity assays.
{"title":"Well-defined palladium Nheterocyclic carbene complexes bearing CF3 moiety: Synthesis, characterization, crystal structure, direct C4-arylation of 3,5-dimethylisoxazole and antioxidant activity","authors":"Ayşegül Kalçık , Nazan Kaloğlu , Serhat Keser , Zarife Sibel Şahin , Serpil Demir Düşünceli","doi":"10.1016/j.jorganchem.2025.123975","DOIUrl":"10.1016/j.jorganchem.2025.123975","url":null,"abstract":"<div><div>A series of palladium <em>N</em>-heterocyclic carbene (NHC) complexes including <em>trans</em>-[Pd(NHC)Br<sub>2</sub>L] (<em>L</em> = C<sub>5</sub>H<sub>5</sub>N, 3-ClC<sub>5</sub>H<sub>4</sub>N, and <em>N</em>-methylimidazole) and [Pd(NHC)<sub>2</sub>Br<sub>2</sub>] have been prepared from {1-(benzyl)-3- (3,5-(bis(trifluoromethyl)benzyl)benzimidazolium bromide}. The structures of these new compounds were confirmed by NMR, FT-IR, and elemental analyses. The crystal structures of the dibromo- [1-(benzyl)-3- (3,5-(bis(trifluoromethyl)benzyl)benzimidazole-2-ylidene]-(pyridine)-palladium(II) and dibromo- [1-(benzyl)-3- (3,5-(bis(trifluoromethyl)benzyl)benzimidazole-2-ylidene]-(<em>N</em>-methylimidazole)-palladium(II) were determined by single-crystal X-ray diffraction. Palladium complexes were developed as efficient pre-catalysts for direct C4-arylation of 3,5-dimethylisoxazole and aryl bromides. Biological efficiency of <em>trans</em>-[Pd(NHC)Br<sub>2</sub>L]was evaluated by antioxidant activities like ABTS, OH and DPPH radical scavenging activity assays.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1045 ","pages":"Article 123975"},"PeriodicalIF":2.1,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748494","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}
Pub Date : 2025-12-04DOI: 10.1016/j.jorganchem.2025.123961
Khadijeh Rabiei
The reactions that create carbon-carbon bonds have consistently fascinated chemists due to their vast spectrum of applications in organic chemistry. In particular, the Suzuki reaction is renowned for forming C–C bonds, which are utilized to prepare a broad spectrum of biological and pharmaceutical compounds. Furthermore, investigators are endeavoring to develop easy, inexpensive, rapid, and more effective procedures in various coupling reactions, with the Suzuki coupling being a widely employed cross-coupling reaction in current organic synthesis. Metal-organic frameworks (MOFs) have emerged as materials that can serve as solid supports with a large surface area, positioning themselves at the forefront of research in catalysis. Over the past years, MOFs have attracted special attention as a type of organic-inorganic-based material, primarily due to their tunable structures and high porosity, which allow for the incorporation of various metal centers. Notably, they have been utilized for numerous organic transformations as eco-friendly replacements for traditional heterogeneous catalysts, achieving satisfactory catalytic performance while enhancing the efficiency of organic conversion processes. The significance of MOFs is expected to be further underscored in the upcoming 2025 Nobel Prize in Chemistry, as their innovative applications in catalysis could revolutionize the field and offer sustainable solutions to traditional chemical processes. Consequently, MOFs could be an excellent support choice for creating ideal metal-based catalysts, which exhibit greater availability of active sites and remarkable catalytic performance. Ultimately, the primary objective of this review is to highlight the utility of MOF-based catalyst systems in the Suzuki reaction for the construction of valuable biaryl compounds, encompassing developments leading up to 2025.
{"title":"Advancing Suzuki couplings: The role of metal-organic frameworks in efficient biaryl compound synthesis","authors":"Khadijeh Rabiei","doi":"10.1016/j.jorganchem.2025.123961","DOIUrl":"10.1016/j.jorganchem.2025.123961","url":null,"abstract":"<div><div>The reactions that create carbon-carbon bonds have consistently fascinated chemists due to their vast spectrum of applications in organic chemistry. In particular, the Suzuki reaction is renowned for forming C–C bonds, which are utilized to prepare a broad spectrum of biological and pharmaceutical compounds. Furthermore, investigators are endeavoring to develop easy, inexpensive, rapid, and more effective procedures in various coupling reactions, with the Suzuki coupling being a widely employed cross-coupling reaction in current organic synthesis. Metal-organic frameworks (MOFs) have emerged as materials that can serve as solid supports with a large surface area, positioning themselves at the forefront of research in catalysis. Over the past years, MOFs have attracted special attention as a type of organic-inorganic-based material, primarily due to their tunable structures and high porosity, which allow for the incorporation of various metal centers. Notably, they have been utilized for numerous organic transformations as eco-friendly replacements for traditional heterogeneous catalysts, achieving satisfactory catalytic performance while enhancing the efficiency of organic conversion processes. The significance of MOFs is expected to be further underscored in the upcoming 2025 Nobel Prize in Chemistry, as their innovative applications in catalysis could revolutionize the field and offer sustainable solutions to traditional chemical processes. Consequently, MOFs could be an excellent support choice for creating ideal metal-based catalysts, which exhibit greater availability of active sites and remarkable catalytic performance. Ultimately, the primary objective of this review is to highlight the utility of MOF-based catalyst systems in the Suzuki reaction for the construction of valuable biaryl compounds, encompassing developments leading up to 2025.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1045 ","pages":"Article 123961"},"PeriodicalIF":2.1,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748495","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}
Magnetic carbon nanotubes (MCNTs) have emerged as a versatile class of nanostructured materials that combine the physicochemical properties of carbon nanotubes with the magnetic responsiveness of incorporated nanoparticles. Their high surface area, tunable surface functionality, excellent thermal and chemical stability, and ease of magnetic separation make them particularly attractive as heterogeneous catalysts. In recent years, MCNTs have been extensively explored in multicomponent reactions (MCRs), a powerful synthetic strategy that enables the rapid and atom‐economical construction of structurally diverse heterocycles with pharmaceutical and agrochemical relevance. This review highlights the design, synthesis, and catalytic applications of MCNTs in MCRs leading to nitrogen-, oxygen-, and sulfur-containing heterocycles reported over the past decade. Special emphasis is placed on how surface functionalization and magnetic modification enhance catalytic efficiency, recyclability, and sustainability. Comparative insights into reaction yields, selectivity, and green chemistry metrics are provided, alongside a discussion of mechanistic aspects and structure–activity relationships. This review explores the design, functionalization, and catalytic applications of magnetic carbon nanotubes (MCNTs) in multicomponent synthesis of heterocycles, emphasizing their efficiency, recyclability, and potential for sustainable chemistry. Finally, current challenges and future perspectives are addressed, particularly the integration of MCNTs in scalable and environmentally benign heterocyclic synthesis.
{"title":"Magnetic carbon nanotubes in multicomponent reactions: A path to sustainable heterocyclic synthesis","authors":"Mohammad Abushuhel , Radwan Ali , Subbulakshmi Ganesan , Al-Hasnaawei Shaker , Mosstafa Kazemi , Karthikeyan Jayabalan , Renu Sharma , Aashna Sinha","doi":"10.1016/j.jorganchem.2025.123971","DOIUrl":"10.1016/j.jorganchem.2025.123971","url":null,"abstract":"<div><div>Magnetic carbon nanotubes (MCNTs) have emerged as a versatile class of nanostructured materials that combine the physicochemical properties of carbon nanotubes with the magnetic responsiveness of incorporated nanoparticles. Their high surface area, tunable surface functionality, excellent thermal and chemical stability, and ease of magnetic separation make them particularly attractive as heterogeneous catalysts. In recent years, MCNTs have been extensively explored in multicomponent reactions (MCRs), a powerful synthetic strategy that enables the rapid and atom‐economical construction of structurally diverse heterocycles with pharmaceutical and agrochemical relevance. This review highlights the design, synthesis, and catalytic applications of MCNTs in MCRs leading to nitrogen-, oxygen-, and sulfur-containing heterocycles reported over the past decade. Special emphasis is placed on how surface functionalization and magnetic modification enhance catalytic efficiency, recyclability, and sustainability. Comparative insights into reaction yields, selectivity, and green chemistry metrics are provided, alongside a discussion of mechanistic aspects and structure–activity relationships. This review explores the design, functionalization, and catalytic applications of magnetic carbon nanotubes (MCNTs) in multicomponent synthesis of heterocycles, emphasizing their efficiency, recyclability, and potential for sustainable chemistry. Finally, current challenges and future perspectives are addressed, particularly the integration of MCNTs in scalable and environmentally benign heterocyclic synthesis.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1045 ","pages":"Article 123971"},"PeriodicalIF":2.1,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748497","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}
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