Pub Date : 2026-03-15Epub Date: 2026-01-30DOI: 10.1016/j.jorganchem.2026.124051
Lokesh Chandrakar, Ramesh Ambatwar, Gopal L. Khatik
A dinuclear copper(I) complex, (nBu4N)2[Cu2I4], was developed and employed as an efficient and air-stable catalyst for azide-alkyne cycloaddition reactions, as a novel exploration of click chemistry for its efficiency, reliability, and regioselectivity. A 20 wt% of the catalyst in a THF: water (1:2, v/v) solvent system was found to be useful for a wide range of terminal alkynes and organic azides to afford the corresponding 1,4-disubstituted 1,2,3-triazoles in excellent yields. This methodology offers several advantages, including using an economic solvent, reduced reaction time, scalability, and high product yields. It demonstrated a remarkable substrate scope and functional group tolerance, including heterocyclic scaffolds such as propargylated piperidine, morpholine, piperazine, and isatin. The mild, ligand-free reaction conditions and the high efficiency and regioselective product highlight its potential for practical applications in synthesizing structurally diverse and medicinally important heterocyclic triazoles.
{"title":"Efficient and recyclable halide-bridged dinuclear copper(I) complex, (nBu4N)2[Cu2I4]- catalyzed greener click reaction for the regio/chemo-selective synthesis of diverse 1,4-disubstituted 1,2,3-triazoles","authors":"Lokesh Chandrakar, Ramesh Ambatwar, Gopal L. Khatik","doi":"10.1016/j.jorganchem.2026.124051","DOIUrl":"10.1016/j.jorganchem.2026.124051","url":null,"abstract":"<div><div>A dinuclear copper(I) complex, (nBu<sub>4</sub>N)<sub>2</sub>[Cu<sub>2</sub>I<sub>4</sub>], was developed and employed as an efficient and air-stable catalyst for azide-alkyne cycloaddition reactions, as a novel exploration of click chemistry for its efficiency, reliability, and regioselectivity. A 20 wt% of the catalyst in a THF: water (1:2, v/v) solvent system was found to be useful for a wide range of terminal alkynes and organic azides to afford the corresponding 1,4-disubstituted 1,2,3-triazoles in excellent yields. This methodology offers several advantages, including using an economic solvent, reduced reaction time, scalability, and high product yields. It demonstrated a remarkable substrate scope and functional group tolerance, including heterocyclic scaffolds such as propargylated piperidine, morpholine, piperazine, and isatin. The mild, ligand-free reaction conditions and the high efficiency and regioselective product highlight its potential for practical applications in synthesizing structurally diverse and medicinally important heterocyclic triazoles.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1048 ","pages":"Article 124051"},"PeriodicalIF":2.1,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146171225","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 : 2026-03-15Epub Date: 2026-01-19DOI: 10.1016/j.jorganchem.2026.124031
Yu-Huei Li , I-Hsuan Fu , Yen-Ming Chen , Hui-Lung Chen , Minghuey Shieh
Efficient synthetic routes to metal carbonyl cluster–based polymers via ion-exchange processes remain unexplored. In this study, a mechanochemical ion-exchange strategy was developed using a one-dimensional (1D) Cu–dpy (dpy = 4,4’-dipyridyl) template polymer, [Cu(dpy)(MeCN)2(BF4)]n, and Hg-bridged iron carbonyl chalcogenide clusters, [Et4N]2[Hg{EFe3(CO)9}2] (E = Te, Se, S), to construct novel polymeric materials. When polymer [Cu(dpy)(MeCN)2(BF4)]n was treated with [Et4N]2[Hg{TeFe3(CO)9}2] in a ratio of 2: 1 via liquid-assisted grinding (LAG), a 1D polymer [{Cu(dpy)(MeCN)2}2{Hg[TeFe3(CO)9]2}]n (1) was obtained. Single-crystal X-ray diffraction showed that polymer 1 consisted of cationic chains [Cu(dpy)(MeCN)2]n and weakly coordinating anions [Hg{TeFe3(CO)9}2]2–. In contrast, when a sulfur-based cluster was used in a similar ion-exchange reaction, the resulting cross-linked 1D polymer [{Cu(dpy)(MeCN)}2{Hg[SFe3(CO)9]2}]n (2) was formed, with the [Hg{SFe3(CO)9}2] moiety serving as a cross-linker via the Cu–S bond. Further, the three-component mechanochemical reactions of [Cu(dpy)(MeCN)2(BF4)]n, chalcogenide clusters [Et4N]2[Hg{EFe3(CO)9}2] (E = Te, Se), and dpy in a ratio of 2:1:0.5 produced the unique 1D/2D-hybrid cation–anion polymers [{Cu(dpy)(MeCN)2}2{Cu(dpy)1.5(MeCN)}2{Hg[EFe3(CO)9]2}2]n (E = Te, 3a; Se, 3b), respectively. Notably, polymer 3a could be obtained by the transformation of polymer 1 with dpy via LAG. Detailed single-crystal X-ray analyses revealed extensive weak intermolecular interactions within these polymeric frameworks. Importantly, the cluster-introduced Cu polymers 1, 2, 3a, and 3b possessed low optical energy gaps in a range of 1.36–1.63 eV, which was significantly lower than the parent polymer [Cu(dpy)(MeCN)2(BF4)]n (2.46 eV). Their efficient electron-transport properties were further investigated through density-of-state (DOS) calculations.
{"title":"Cu–dipyridyl polymers incorporating weakly coordinating E–Fe–Hg–CO (E = Te, Se, S) clusters: Mechanochemical anion-exchange, cluster-induced framework transformations, and semiconducting properties","authors":"Yu-Huei Li , I-Hsuan Fu , Yen-Ming Chen , Hui-Lung Chen , Minghuey Shieh","doi":"10.1016/j.jorganchem.2026.124031","DOIUrl":"10.1016/j.jorganchem.2026.124031","url":null,"abstract":"<div><div>Efficient synthetic routes to metal carbonyl cluster–based polymers <em>via</em> ion-exchange processes remain unexplored. In this study, a mechanochemical ion-exchange strategy was developed using a one-dimensional (1D) Cu–dpy (dpy = 4,4’-dipyridyl) template polymer, [Cu(dpy)(MeCN)<sub>2</sub>(BF<sub>4</sub>)]<em><sub>n</sub></em>, and Hg-bridged iron carbonyl chalcogenide clusters, [Et<sub>4</sub>N]<sub>2</sub>[Hg{EFe<sub>3</sub>(CO)<sub>9</sub>}<sub>2</sub>] (E = Te, Se, S), to construct novel polymeric materials. When polymer [Cu(dpy)(MeCN)<sub>2</sub>(BF<sub>4</sub>)]<em><sub>n</sub></em> was treated with [Et<sub>4</sub>N]<sub>2</sub>[Hg{TeFe<sub>3</sub>(CO)<sub>9</sub>}<sub>2</sub>] in a ratio of 2: 1 <em>via</em> liquid-assisted grinding (LAG), a 1D polymer [{Cu(dpy)(MeCN)<sub>2</sub>}<sub>2</sub>{Hg[TeFe<sub>3</sub>(CO)<sub>9</sub>]<sub>2</sub>}]<em><sub>n</sub></em> (<strong>1</strong>) was obtained. Single-crystal X-ray diffraction showed that polymer <strong>1</strong> consisted of cationic chains [Cu(dpy)(MeCN)<sub>2</sub>]<em><sub>n</sub></em> and weakly coordinating anions [Hg{TeFe<sub>3</sub>(CO)<sub>9</sub>}<sub>2</sub>]<sup>2–</sup>. In contrast, when a sulfur-based cluster was used in a similar ion-exchange reaction, the resulting cross-linked 1D polymer [{Cu(dpy)(MeCN)}<sub>2</sub>{Hg[SFe<sub>3</sub>(CO)<sub>9</sub>]<sub>2</sub>}]<em><sub>n</sub></em> (<strong>2</strong>) was formed, with the [Hg{SFe<sub>3</sub>(CO)<sub>9</sub>}<sub>2</sub>] moiety serving as a cross-linker <em>via</em> the Cu–S bond. Further, the three-component mechanochemical reactions of [Cu(dpy)(MeCN)<sub>2</sub>(BF<sub>4</sub>)]<em><sub>n</sub></em>, chalcogenide clusters [Et<sub>4</sub>N]<sub>2</sub>[Hg{EFe<sub>3</sub>(CO)<sub>9</sub>}<sub>2</sub>] (E = Te, Se), and dpy in a ratio of 2:1:0.5 produced the unique 1D/2D-hybrid cation–anion polymers [{Cu(dpy)(MeCN)<sub>2</sub>}<sub>2</sub>{Cu(dpy)<sub>1.5</sub>(MeCN)}<sub>2</sub>{Hg[EFe<sub>3</sub>(CO)<sub>9</sub>]<sub>2</sub>}<sub>2</sub>]<em><sub>n</sub></em> (E = Te, <strong>3a</strong>; Se, <strong>3b</strong>), respectively. Notably, polymer <strong>3a</strong> could be obtained by the transformation of polymer <strong>1</strong> with dpy <em>via</em> LAG. Detailed single-crystal X-ray analyses revealed extensive weak intermolecular interactions within these polymeric frameworks. Importantly, the cluster-introduced Cu polymers <strong>1, 2, 3a</strong>, and <strong>3b</strong> possessed low optical energy gaps in a range of 1.36–1.63 eV, which was significantly lower than the parent polymer [Cu(dpy)(MeCN)<sub>2</sub>(BF<sub>4</sub>)]<em><sub>n</sub></em> (2.46 eV). Their efficient electron-transport properties were further investigated through density-of-state (DOS) calculations.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1048 ","pages":"Article 124031"},"PeriodicalIF":2.1,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076036","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 : 2026-03-15Epub Date: 2026-01-25DOI: 10.1016/j.jorganchem.2026.124041
Ingo Ott
Gold complexes with N-heterocyclic carbene (NHC) ligands have been intensively studied as new anticancer agents, while other biomedical and therapeutic applications have been less frequently explored. In this review the antibacterial properties of gold NHC complexes are summarised. In particular monocarbene complexes of the type (NHC)Au(Ⅰ)Cl have demonstrated considerable antibacterial activity with preference for Gram-positive bacteria. The inhibition of bacterial thioredoxin reductase, biofilm eradication and membrane damage have been experimentally confirmed for several examples and unwanted toxicity against eukaryotic cells could be reduced by bioconjugation or formation of hybrid agents with antibiotics. In summary, gold NHC complexes represent a new type of antibacterial agent with promising potential for antibiotic drug development.
{"title":"Recent developments on gold N-heterocyclic carbene complexes as antibacterial tool compounds and potential antibiotics","authors":"Ingo Ott","doi":"10.1016/j.jorganchem.2026.124041","DOIUrl":"10.1016/j.jorganchem.2026.124041","url":null,"abstract":"<div><div>Gold complexes with N-heterocyclic carbene (NHC) ligands have been intensively studied as new anticancer agents, while other biomedical and therapeutic applications have been less frequently explored. In this review the antibacterial properties of gold NHC complexes are summarised. In particular monocarbene complexes of the type (NHC)Au(Ⅰ)Cl have demonstrated considerable antibacterial activity with preference for Gram-positive bacteria. The inhibition of bacterial thioredoxin reductase, biofilm eradication and membrane damage have been experimentally confirmed for several examples and unwanted toxicity against eukaryotic cells could be reduced by bioconjugation or formation of hybrid agents with antibiotics. In summary, gold NHC complexes represent a new type of antibacterial agent with promising potential for antibiotic drug development.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1048 ","pages":"Article 124041"},"PeriodicalIF":2.1,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076034","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 : 2026-03-15Epub Date: 2026-01-29DOI: 10.1016/j.jorganchem.2026.124048
Viktoria Ebel, Marcel Geppert, Niklas Bauch, Michael Linseis, Rainer F. Winter
We report on the synthesis and characterization of two new macrocyclic, rectangular tetrarhenium complexes resulting from the {Re(CO)3}2(2,2′-bis(benzimidazolate)) precursor {Re(CO)3}2(BiBzIm) and the core-rigidified 4,4′-bipyridine-type bridging ligands thieno[2,3-c:5,4-c']dipyridine (complex 2a) or 9-(4-methylthiophenyl)-9H-pyrrolo[2,3-c:5,4-c']dipyridine (complex 2b). Both complexes undergo four consecutive one-electron reductions which are all centered on the diimine ligands. Redox splittings of the first pair of reductions are traced to electronic coupling in the mixed-valent state where the charges at the two diimine ligands, 0 and −1, (formally) differ. IR and UV/vis/NIR spectroscopic investigations on the neutral, the one-, and the two-electron reduced forms of these complexes characterize the singly reduced monoanions as moderately strongly coupled mixed-valent systems of Class II. Interestingly, the charge distribution parameter Δρ derived from IR spectroscopy of ca. 0.25 is roughly twice as large as the optically derived values of Hush´s delocalization parameter α. Complexes 2a,b are strongly phosphorescent at 77 K, with quantum yields of 62% for 2a and 91% for 2b Phosphorescence is retained at r. t., albeit with significantly reduced quantum yields of 1.1% and 2.0%, respectively.
{"title":"New phosphorescent supramolecular Re-rectangles and their mixed-valent anions","authors":"Viktoria Ebel, Marcel Geppert, Niklas Bauch, Michael Linseis, Rainer F. Winter","doi":"10.1016/j.jorganchem.2026.124048","DOIUrl":"10.1016/j.jorganchem.2026.124048","url":null,"abstract":"<div><div>We report on the synthesis and characterization of two new macrocyclic, rectangular tetrarhenium complexes resulting from the {<em>Re</em>(CO)<sub>3</sub>}<sub>2</sub>(2,2′-bis(benzimidazolate)) precursor {<em>Re</em>(CO)<sub>3</sub>}<sub>2</sub>(BiBzIm) and the core-rigidified 4,4′-bipyridine-type bridging ligands thieno[2,3-c:5,4-c']dipyridine (complex <strong>2a</strong>) or 9-(4-methylthiophenyl)-9H-pyrrolo[2,3-c:5,4-c']dipyridine (complex <strong>2b</strong>). Both complexes undergo four consecutive one-electron reductions which are all centered on the diimine ligands. Redox splittings of the first pair of reductions are traced to electronic coupling in the mixed-valent state where the charges at the two diimine ligands, 0 and −1, (formally) differ. IR and UV/vis/NIR spectroscopic investigations on the neutral, the one-, and the two-electron reduced forms of these complexes characterize the singly reduced monoanions as moderately strongly coupled mixed-valent systems of Class II. Interestingly, the charge distribution parameter Δ<em>ρ</em> derived from IR spectroscopy of ca. 0.25 is roughly twice as large as the optically derived values of Hush´s delocalization parameter α. Complexes <strong>2a,b</strong> are strongly phosphorescent at 77 K, with quantum yields of 62% for <strong>2a</strong> and 91% for <strong>2b</strong> Phosphorescence is retained at r. t., albeit with significantly reduced quantum yields of 1.1% and 2.0%, respectively.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1048 ","pages":"Article 124048"},"PeriodicalIF":2.1,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146171224","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 magnetically recoverable nanocatalyst, CoFe₂O₄@CNSCu, was prepared via a three-step procedure: (i) co-precipitation synthesis of CoFe₂O₄ nanoparticles, (ii) coating with HKUST-1 through a mercaptoacetic acid linker, and (iii) formation of a carbon–sulfur framework from thioacetamide under nitrogen. The catalyst was fully characterized by XRD, FE-SEM, and TEM. It was applied in a three-component reaction for the synthesis of novel triazole-based hybrids containing either 2-phenyl-2,3-dihydro-phthalazine-1,4‑dione or benzofuran units. Under optimized conditions (5 mol% catalyst, DMSO/H₂O 1:1, room temperature, 1 h), a wide range of products were obtained in good to excellent isolated yields (61–96%) and high purity. The CoFe₂O₄@CNSCu nanocatalyst efficiently generates Cu(I) active species in situ, enabling smooth 1,3-dipolar cycloaddition while allowing easy magnetic separation and reuse. The method tolerated various alkyl halides, including electron-donating, electron-withdrawing, and sterically demanding groups, highlighting its generality and practical applicability. Preliminary biological evaluation revealed that the new hybrids strongly inhibited PARP-1, suggesting their potential as promising leads for anticancer drug development.
{"title":"Design and synthesis of novel phthalazine and benzofuran scaffolds using CoFe₂O₄@CNSCu nanocatalyst: Evaluation of PARP-1 inhibitory activity","authors":"Firouz Matloubi Moghaddam, Hassan Fazli, Shaghayegh Sadredini","doi":"10.1016/j.jorganchem.2025.123997","DOIUrl":"10.1016/j.jorganchem.2025.123997","url":null,"abstract":"<div><div>A magnetically recoverable nanocatalyst, CoFe₂O₄@CNSCu, was prepared via a three-step procedure: (i) co-precipitation synthesis of CoFe₂O₄ nanoparticles, (ii) coating with HKUST-1 through a mercaptoacetic acid linker, and (iii) formation of a carbon–sulfur framework from thioacetamide under nitrogen. The catalyst was fully characterized by XRD, FE-SEM, and TEM. It was applied in a three-component reaction for the synthesis of novel triazole-based hybrids containing either 2-phenyl-2,3-dihydro-phthalazine-1,4‑dione or benzofuran units. Under optimized conditions (5 mol% catalyst, DMSO/H₂O 1:1, room temperature, 1 h), a wide range of products were obtained in good to excellent isolated yields (61–96%) and high purity. The CoFe₂O₄@CNSCu nanocatalyst efficiently generates Cu(I) active species in situ, enabling smooth 1,3-dipolar cycloaddition while allowing easy magnetic separation and reuse. The method tolerated various alkyl halides, including electron-donating, electron-withdrawing, and sterically demanding groups, highlighting its generality and practical applicability. Preliminary biological evaluation revealed that the new hybrids strongly inhibited PARP-1, suggesting their potential as promising leads for anticancer drug development.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1047 ","pages":"Article 123997"},"PeriodicalIF":2.1,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145924561","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}
In this research, a new and eco-friendly way is described to produce palladium nanoparticles (Pd NPs) that immobilized on graphene oxide using fruit extract of Lycium Barbarum (LB). The GO/Pd NPs was developed by attach the bio-component of the fruit extract of LB and the bio-reduction of palladium ions to palladium nanoparticles over the graphene oxide. Various techniques like TEM, FE-SEM, EDX, ICP-OES, XRD, and elemental mapping were applied to analyze the prepared nanomaterial. As showed by TEM picture, the Pd NPs were evenly sized, round, and about 20 to 30 nanometers wide. The catalytic activity of this easily separable magnetized heterogeneous GO/Pd NPs nanocomposite was successfully examined in the C–N coupling condensation through Buchwald–Hartwig process. Different aryl amines were created by reacting halo arenes (like iodides, bromides, and chlorides) with amines, achieving in good yields. The catalyst can be recycled well even after up to 8 times without drop in its effectiveness.
{"title":"Green decorated palladium nanoparticles over the surface of graphene oxide: An efficient catalyst for Buchwald–Hartwig C–N cross coupling reactions","authors":"Qamar Abuhassan , Supriya S , Subhashree Ray , Renu Sharma , Ahmed Aldulaimi , Omayma Salim Waleed , Rafid Jihad Albadr , Mariem Alwan , Dmitriy Bystrov , Ruslanbek Siddikov , Sardor Sabirov , Aseel Smerat","doi":"10.1016/j.jorganchem.2026.124023","DOIUrl":"10.1016/j.jorganchem.2026.124023","url":null,"abstract":"<div><div>In this research, a new and eco-friendly way is described to produce palladium nanoparticles (Pd NPs) that immobilized on graphene oxide using fruit extract of <em>Lycium Barbarum</em> (LB). The GO/Pd NPs was developed by attach the bio-component of the fruit extract of <em>LB</em> and the bio-reduction of palladium ions to palladium nanoparticles over the graphene oxide. Various techniques like TEM, FE-SEM, EDX, ICP-OES, XRD, and elemental mapping were applied to analyze the prepared nanomaterial. As showed by TEM picture, the Pd NPs were evenly sized, round, and about 20 to 30 nanometers wide. The catalytic activity of this easily separable magnetized heterogeneous GO/Pd NPs nanocomposite was successfully examined in the C–N coupling condensation through Buchwald–Hartwig process. Different aryl amines were created by reacting halo arenes (like iodides, bromides, and chlorides) with amines, achieving in good yields. The catalyst can be recycled well even after up to 8 times without drop in its effectiveness.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1047 ","pages":"Article 124023"},"PeriodicalIF":2.1,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975505","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 : 2026-03-01Epub Date: 2026-01-03DOI: 10.1016/j.jorganchem.2026.124010
Mohamed Abu Shuheil , Magdi E.A. Zaki , G. Padma Priya , Qusay Husam Aziz , Y. Sasikumar , Ahmed Aldulaimi , Renu Sharma , Sobhi M. Gomha , Mosstafa Kazemi
A novel heterogeneous palladium catalyst, MWCNTs/MNPs–TAEA–Phen–Pd(0), was developed and applied for the efficient synthesis of diaryl ketones via carbonylative Suzuki–Miyaura coupling reactions. The MWCNTs/MNPs–TAEA–Phen–Pd(0) catalyst integrates multi-walled carbon nanotubes (MWCNTs) and magnetic nanoparticles (Fe₃O₄) functionalized with tris(2-aminoethyl)amine (TAEA) and 1,10-phenanthroline (Phen) ligands, providing high dispersion and stabilization of Pd(0) species. Under optimized conditions, a wide variety of aryl iodides and arylboronic acids were successfully transformed into the corresponding diaryl ketones in excellent yields (79–98%), demonstrating broad substrate tolerance toward both electron-donating and electron-withdrawing substituents. The MWCNTs/MNPs–TAEA–Phen–Pd(0) catalyst exhibited outstanding recyclability, maintaining 90% yield after seven consecutive runs, as confirmed by SEM, FT-IR, XRD, ICP-OES and VSM analyses. Significant advantages of this system include high catalytic activity, easy magnetic separation, robust stability, and eco-friendly reaction conditions using a ChCl–glycerol solvent system. These results establish MWCNTs/MNPs–TAEA–Phen–Pd(0) as an efficient, durable, and magnetically separable nanocatalyst for sustainable carbonylative coupling reactions, providing a green and practical alternative to conventional homogeneous palladium systems.
{"title":"High-yielding preparation of Diaryl ketones via carbonylative cross-coupling reactions using a magnetic/carbon nanotube supported palladium catalyst in DESs solvent","authors":"Mohamed Abu Shuheil , Magdi E.A. Zaki , G. Padma Priya , Qusay Husam Aziz , Y. Sasikumar , Ahmed Aldulaimi , Renu Sharma , Sobhi M. Gomha , Mosstafa Kazemi","doi":"10.1016/j.jorganchem.2026.124010","DOIUrl":"10.1016/j.jorganchem.2026.124010","url":null,"abstract":"<div><div>A novel heterogeneous palladium catalyst, MWCNTs/MNPs–TAEA–Phen–Pd(0), was developed and applied for the efficient synthesis of diaryl ketones via carbonylative Suzuki–Miyaura coupling reactions. The MWCNTs/MNPs–TAEA–Phen–Pd(0) catalyst integrates multi-walled carbon nanotubes (MWCNTs) and magnetic nanoparticles (Fe₃O₄) functionalized with tris(2-aminoethyl)amine (TAEA) and 1,10-phenanthroline (Phen) ligands, providing high dispersion and stabilization of Pd(0) species. Under optimized conditions, a wide variety of aryl iodides and arylboronic acids were successfully transformed into the corresponding diaryl ketones in excellent yields (79–98%), demonstrating broad substrate tolerance toward both electron-donating and electron-withdrawing substituents. The MWCNTs/MNPs–TAEA–Phen–Pd(0) catalyst exhibited outstanding recyclability, maintaining 90% yield after seven consecutive runs, as confirmed by SEM, FT-IR, XRD, ICP-OES and VSM analyses. Significant advantages of this system include high catalytic activity, easy magnetic separation, robust stability, and eco-friendly reaction conditions using a ChCl–glycerol solvent system. These results establish MWCNTs/MNPs–TAEA–Phen–Pd(0) as an efficient, durable, and magnetically separable nanocatalyst for sustainable carbonylative coupling reactions, providing a green and practical alternative to conventional homogeneous palladium systems.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1047 ","pages":"Article 124010"},"PeriodicalIF":2.1,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145924558","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 : 2026-03-01Epub Date: 2026-01-07DOI: 10.1016/j.jorganchem.2026.124012
Alexander V. Grishin , Elena V. Sazonova , Nikolay V. Somov , Svetlana V. Baryshnikova , Andrey Yu. Shishkin , Vasily F. Smirnov , Natalia Yu. Grishina
The series of new (η6-arene)tricarbonylchromium π-complexes were obtained by the reaction of 3-phenyl-3,4-dihydro-2Н-1,3-benzoxazine (1), 3,4-dihydro-2Н-1,4-benzoxazine (2) and 3-phenyl-3,4-dihydro-2Н-1,4-benzoxazine (3) with triammine(tricarbonyl)chromium (4) in refluxing dioxane. It was found out that in the case of the 1,3-benzoxazine ligand 1 the coordination of tricarbonylchromium group occurs via phenyl substituent. It was shown that processes involving 1,4-benzoxazine derivatives 2, 3 are characterized by coordination of tricarbonylchromium group on phenylene fragment. The novel compounds were characterized by UV–vis, IR, NMR spectroscopy, mass spectrometry, HPLC. The performed single-crystal X-ray diffraction studies confirmed the formation of complexes via η6-coordination of aromatic fragments of benzoxazine ligands by chromium atom.
{"title":"The synthesis of (η6-arene)tricarbonylchromium complexes of dihydro derivatives of 1,3- and 1,4-benzoxazines","authors":"Alexander V. Grishin , Elena V. Sazonova , Nikolay V. Somov , Svetlana V. Baryshnikova , Andrey Yu. Shishkin , Vasily F. Smirnov , Natalia Yu. Grishina","doi":"10.1016/j.jorganchem.2026.124012","DOIUrl":"10.1016/j.jorganchem.2026.124012","url":null,"abstract":"<div><div>The series of new (η<sup>6</sup>-arene)tricarbonylchromium π-complexes were obtained by the reaction of 3-phenyl-3,4-dihydro-2<em>Н</em>-1,3-benzoxazine (1), 3,4-dihydro-2<em>Н</em>-1,4-benzoxazine (2) and 3-phenyl-3,4-dihydro-2<em>Н</em>-1,4-benzoxazine (3) with triammine(tricarbonyl)chromium (4) in refluxing dioxane. It was found out that in the case of the 1,3-benzoxazine ligand 1 the coordination of tricarbonylchromium group occurs via phenyl substituent. It was shown that processes involving 1,4-benzoxazine derivatives 2, 3 are characterized by coordination of tricarbonylchromium group on phenylene fragment. The novel compounds were characterized by UV–vis, IR, NMR spectroscopy, mass spectrometry, HPLC. The performed single-crystal X-ray diffraction studies confirmed the formation of complexes via η<sup>6</sup>-coordination of aromatic fragments of benzoxazine ligands by chromium atom.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1047 ","pages":"Article 124012"},"PeriodicalIF":2.1,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975503","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}
The increasing atmospheric concentration of carbon dioxide (CO₂) has stimulated considerable interest in its chemical fixation to produce value-added products. In this study, two novel azo-Schiff base ligands were synthesized from salicylaldehyde derivatives and subsequently coordinated with palladium(II) to afford stable Pd(II) complexes. The complexes were characterized comprehensively using elemental analysis, FT-IR, UV–Vis, NMR, and high-resolution mass spectrometry (HRMS), confirming the successful formation of the desired coordination frameworks. Their catalytic performances were systematically investigated in the cycloaddition reaction of CO₂ with various epoxides under both atmospheric and high-pressure conditions. The results revealed that the Pd(II) complexes exhibit high activity and selectivity toward cyclic carbonate formation, with yields exceeding 90% under optimized conditions. The azo functionality in the Schiff base ligands was found to play a crucial role in modulating the electronic environment around the Pd(II) center, thereby enhancing catalytic efficiency. This work highlights the potential of azo-Schiff base Pd(II) complexes as promising homogeneous catalysts for sustainable CO₂ utilization and provides new insights into ligand design strategies for efficient CO₂ fixation.
{"title":"Schiff base Pd(II) complexes as efficient catalysts for CO₂ conversion to cyclic carbonates under high and atmospheric pressure","authors":"Ayşe Kazancı Dağ , Emine Aytar , Ayşegül Köse , Esin Ispir","doi":"10.1016/j.jorganchem.2026.124028","DOIUrl":"10.1016/j.jorganchem.2026.124028","url":null,"abstract":"<div><div>The increasing atmospheric concentration of carbon dioxide (CO₂) has stimulated considerable interest in its chemical fixation to produce value-added products. In this study, two novel azo-Schiff base ligands were synthesized from salicylaldehyde derivatives and subsequently coordinated with palladium(II) to afford stable Pd(II) complexes. The complexes were characterized comprehensively using elemental analysis, FT-IR, UV–Vis, NMR, and high-resolution mass spectrometry (HRMS), confirming the successful formation of the desired coordination frameworks. Their catalytic performances were systematically investigated in the cycloaddition reaction of CO₂ with various epoxides under both atmospheric and high-pressure conditions. The results revealed that the Pd(II) complexes exhibit high activity and selectivity toward cyclic carbonate formation, with yields exceeding 90% under optimized conditions. The azo functionality in the Schiff base ligands was found to play a crucial role in modulating the electronic environment around the Pd(II) center, thereby enhancing catalytic efficiency. This work highlights the potential of azo-Schiff base Pd(II) complexes as promising homogeneous catalysts for sustainable CO₂ utilization and provides new insights into ligand design strategies for efficient CO₂ fixation.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1047 ","pages":"Article 124028"},"PeriodicalIF":2.1,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146024051","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 : 2026-03-01Epub Date: 2026-01-13DOI: 10.1016/j.jorganchem.2026.124022
Samar Naser Mohammed , Mohammed Faiad Naief , Ahmed Mishaal Mohammed , Ahmed M. Alkaoud , M.H. Eisa , Asmiet Ramizy
Monitoring and controlling hazardous gases is of paramount importance because they cause major public health problems, such as cardiovascular disease, respiratory disease, central nervous system disorders, and other illnesses. The NO2 and NH3 gases are connected to global warming, which in turn affects the environment. Therefore, hazardous emissions should be reduced and eliminated. In this study, AuNPs were synthesized using green chemistry, and then combined with MWCNTs synthesized from agricultural byproducts using an ultrasonic probe approach to develop MWCNT-Au nanocomposite. The nanomaterials were examined using FESEM, TEM, XRD, FTIR, and Raman spectroscopy. The MWCNT-Au gas sensor was tested against NO2 and NH3 gases. The results showed that for both gases, the best resistance response as a function of time was recorded at 25 °C° and a concentration of 100 ppm, while the highest sensitivity values were recorded at 25 °C and 150 °C, respectively. Low response and recovery times were observed for NO2 gas at 150 °C and 200 °C, and for NH3 at 25 °C and 200 °C, respectively. These findings demonstrate that the addition of Au-NPs to the surface of MWCNTs increased their conductivity to both reducing and oxidizing gases. The Langmuir KL and qmax values for NO2 and NH3 were 134.1 mg/g, 0.058 L/mg, 100.7 mg/g, and 0.062 L/mg, respectively. In contrast, the Freundlich Kf and n values for NO2 and NH3 were 16.3, 14.7, 2.1, and 2.3, respectively.
{"title":"High-performance NH₃ and NO₂ gas sensing using synthesized MWCNT-Au nanocomposites","authors":"Samar Naser Mohammed , Mohammed Faiad Naief , Ahmed Mishaal Mohammed , Ahmed M. Alkaoud , M.H. Eisa , Asmiet Ramizy","doi":"10.1016/j.jorganchem.2026.124022","DOIUrl":"10.1016/j.jorganchem.2026.124022","url":null,"abstract":"<div><div>Monitoring and controlling hazardous gases is of paramount importance because they cause major public health problems, such as cardiovascular disease, respiratory disease, central nervous system disorders, and other illnesses. The NO<sub>2</sub> and NH<sub>3</sub> gases are connected to global warming, which in turn affects the environment. Therefore, hazardous emissions should be reduced and eliminated. In this study, AuNPs were synthesized using green chemistry, and then combined with MWCNTs synthesized from agricultural byproducts using an ultrasonic probe approach to develop MWCNT-Au nanocomposite. The nanomaterials were examined using FESEM, TEM, XRD, FTIR, and Raman spectroscopy. The MWCNT-Au gas sensor was tested against NO<sub>2</sub> and NH<sub>3</sub> gases. The results showed that for both gases, the best resistance response as a function of time was recorded at 25 °C° and a concentration of 100 ppm, while the highest sensitivity values were recorded at 25 °C and 150 °C, respectively. Low response and recovery times were observed for NO<sub>2</sub> gas at 150 °C and 200 °C, and for NH<sub>3</sub> at 25 °C and 200 °C, respectively. These findings demonstrate that the addition of Au-NPs to the surface of MWCNTs increased their conductivity to both reducing and oxidizing gases. The Langmuir KL and q<sub>max</sub> values for NO<sub>2</sub> and NH<sub>3</sub> were 134.1 mg/g, 0.058 L/mg, 100.7 mg/g, and 0.062 L/mg, respectively. In contrast, the Freundlich K<sub>f</sub> and n values for NO<sub>2</sub> and NH<sub>3</sub> were 16.3, 14.7, 2.1, and 2.3, respectively.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1047 ","pages":"Article 124022"},"PeriodicalIF":2.1,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975504","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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