Pub Date : 2026-04-01Epub Date: 2026-01-28DOI: 10.1016/j.jorganchem.2026.124042
Jia Ji , Xuan Lv , Wen-Qian Deng , Lin Tian , Teng-Qi Yao , Wen-Jing Shi , Da-Hui Wang , Qing Li , Yin-Ling Hou , Ming Fang
Herein, two tetranuclear Ni(II)-based compounds formulated as [Ni4(L1)4(CH3OH)4] (1) and [Ni4(L2)4(CH3OH)4] (2) (H2L1 = (E)-4‑bromo-2-(((5‑chloro-2-(hydroxymethyl)phenyl)imino)methyl)phenol, and H2L2 = (E)-4‑bromo-2-(((2-(hydroxymethyl)phenyl)imino)methyl)phenol) have been obtained by using two different Schiff-base ligands via solvothermal method. Single crystal X-ray diffraction analysis shows that the structures of the two tetranuclear compounds (1 and 2) are mainly composed of four Ni(II) ions, four L12-/L22-, and four coordinated CH3OH, and the four central Ni(II) ions are bridged by four μ3O atoms forming a cubane Ni4O4 core. Notably, compounds 1 and 2 exhibit outstanding catalytic performance for the cycloaddition of CO2 and epoxides under mild conditions. Among them, compound 1 exhibit the highest catalytic efficiency for substrate 2-(bromomethyl)oxirane, with a corresponding yield of up to 98 %; while for substrate 2-(tert‑butoxymethyl)oxirane, which shows relatively lower catalytic activity, the yield can still reach 84 %. What's more, compound 1 as heterogenous catalyst can be reused at least five times without obvious loss in catalytic activity for the cycloaddition reaction.
{"title":"Two tetranuclear Ni(II)-based compounds with a cubane Ni4O4 core: Efficient conversion of CO2 to cyclic carbonates","authors":"Jia Ji , Xuan Lv , Wen-Qian Deng , Lin Tian , Teng-Qi Yao , Wen-Jing Shi , Da-Hui Wang , Qing Li , Yin-Ling Hou , Ming Fang","doi":"10.1016/j.jorganchem.2026.124042","DOIUrl":"10.1016/j.jorganchem.2026.124042","url":null,"abstract":"<div><div>Herein, two tetranuclear Ni(II)-based compounds formulated as [Ni<sub>4</sub>(L<sub>1</sub>)<sub>4</sub>(CH<sub>3</sub>OH)<sub>4</sub>] (<strong>1</strong>) and [Ni<sub>4</sub>(L<sub>2</sub>)<sub>4</sub>(CH<sub>3</sub>OH)<sub>4</sub>] (<strong>2</strong>) (H<sub>2</sub>L<sub>1</sub> = (E)-4‑bromo-2-(((5‑chloro-2-(hydroxymethyl)phenyl)imino)methyl)phenol, and H<sub>2</sub>L<sub>2</sub> = (E)-4‑bromo-2-(((2-(hydroxymethyl)phenyl)imino)methyl)phenol) have been obtained by using two different Schiff-base ligands via solvothermal method. Single crystal X-ray diffraction analysis shows that the structures of the two tetranuclear compounds (<strong>1</strong> and <strong>2)</strong> are mainly composed of four Ni(II) ions, four L<sub>1</sub><sup>2-</sup>/L<sub>2</sub><sup>2-</sup>, and four coordinated CH<sub>3</sub>OH, and the four central Ni(II) ions are bridged by four <em>μ</em><sub>3<img></sub>O atoms forming a cubane Ni<sub>4</sub>O<sub>4</sub> core. Notably, compounds <strong>1</strong> and <strong>2</strong> exhibit outstanding catalytic performance for the cycloaddition of CO<sub>2</sub> and epoxides under mild conditions. Among them, compound <strong>1</strong> exhibit the highest catalytic efficiency for substrate 2-(bromomethyl)oxirane, with a corresponding yield of up to 98 %; while for substrate 2-(tert‑butoxymethyl)oxirane, which shows relatively lower catalytic activity, the yield can still reach 84 %. What's more, compound <strong>1</strong> as heterogenous catalyst can be reused at least five times without obvious loss in catalytic activity for the cycloaddition reaction.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1049 ","pages":"Article 124042"},"PeriodicalIF":2.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122697","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 : 2026-04-01Epub Date: 2026-02-02DOI: 10.1016/j.jorganchem.2026.124053
Mitat Akkoç , Belgin Önder , Enes Evren , Emine Özge Karaca , Nevin Gürbüz , İsmail Özdemir
This study reports the synthesis of novel N-heterocyclic carbene (NHC) ligated silver(I) complexes, which are gaining increasing attention as versatile catalysts in organic synthesis. The structural properties of the synthesized compounds were elucidated in detail using various spectroscopic and thermal analysis techniques, including FTIR, NMR spectroscopy, and melting point determination. These analyses confirmed the successful formation of the complexes and verified that they exhibited the expected molecular structures. The low cost and unique chemical properties of silver make it an attractive alternative to other transition metals. In this context, the catalytic potential of the synthesized Ag-NHC complexes was investigated in the A³ coupling reaction, a key method for the synthesis of propargylamines. The A³ reaction is a crucial step in the formation of nitrogen-containing compounds of significant importance in pharmaceutical and natural product chemistry. Experimental results demonstrated that the Ag-NHC complexes effectively catalyzed the reaction, leading to high yields. In conclusion, this research successfully achieved the synthesis and characterization of new Ag-NHC complexes. Following the acquisition of structural analysis data, their catalytic activity in the A³ coupling reaction was successfully investigated.
{"title":"Systematic study on the catalytic performance of NHC-ligated silver(I) complexes","authors":"Mitat Akkoç , Belgin Önder , Enes Evren , Emine Özge Karaca , Nevin Gürbüz , İsmail Özdemir","doi":"10.1016/j.jorganchem.2026.124053","DOIUrl":"10.1016/j.jorganchem.2026.124053","url":null,"abstract":"<div><div>This study reports the synthesis of novel N-heterocyclic carbene (NHC) ligated silver(I) complexes, which are gaining increasing attention as versatile catalysts in organic synthesis. The structural properties of the synthesized compounds were elucidated in detail using various spectroscopic and thermal analysis techniques, including FTIR, NMR spectroscopy, and melting point determination. These analyses confirmed the successful formation of the complexes and verified that they exhibited the expected molecular structures. The low cost and unique chemical properties of silver make it an attractive alternative to other transition metals. In this context, the catalytic potential of the synthesized Ag-NHC complexes was investigated in the A³ coupling reaction, a key method for the synthesis of propargylamines. The A³ reaction is a crucial step in the formation of nitrogen-containing compounds of significant importance in pharmaceutical and natural product chemistry. Experimental results demonstrated that the Ag-NHC complexes effectively catalyzed the reaction, leading to high yields. In conclusion, this research successfully achieved the synthesis and characterization of new Ag-NHC complexes. Following the acquisition of structural analysis data, their catalytic activity in the A³ coupling reaction was successfully investigated.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1049 ","pages":"Article 124053"},"PeriodicalIF":2.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122698","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: 2026-01-22DOI: 10.1016/j.jorganchem.2026.124032
Sarah K. Dunn, Ashley K. Archambeau, Payne R. Rodriguez, Cynthia B. Powell, Gregory L. Powell
Three novel dinuclear osmium complexes with one bridging and one terminal hydride ligand are synthesized by heating a mixture of Os3(CO)12 and 3,5-dimethylpyrazole (Me2PzH) with microwave radiation. Two trinuclear complexes and a fourth dinuclear complex are also produced. Dimethylpyrazolato (Me2Pz–) ligands bridge two Os atoms in each complex. The trinuclear products Os3(μ-H)(μ-Me2Pz)(CO)10 (1) and Os3(μ-H)2(μ-Me2Pz)2(CO)8 (2) are produced by oxidative addition to Os3(CO)12 of one and two equivalents of Me2PzH, respectively. The dinuclear product Os2(μ-Me2Pz)2(CO)6 (3), a sawhorse complex that was the intended target of the reaction, is isolated in low yield. The dinuclear dihydride products are Os2(μ-H)(μ-Me2Pz)2(H)(CO)5 (4) and two isomers of Os2(μ-H)(μ-Me2Pz)2(H)(CO)4(Me2PzH), one of which (5a) has a Me2PzH ligand trans to the bridging hydride and the other of which (5b) has a Me2PzH ligand trans to an N atom of one of the pyrazolato ligands. Complex 5a is the major product. The Os2 dihydrides represent a new class of diosmium carbonyl complexes. All products were structurally characterized by SC-XRD.*
{"title":"Diosmium dihydride complexes from the reaction of Os3(CO)12 with 3,5-dimethylpyrazole","authors":"Sarah K. Dunn, Ashley K. Archambeau, Payne R. Rodriguez, Cynthia B. Powell, Gregory L. Powell","doi":"10.1016/j.jorganchem.2026.124032","DOIUrl":"10.1016/j.jorganchem.2026.124032","url":null,"abstract":"<div><div>Three novel dinuclear osmium complexes with one bridging and one terminal hydride ligand are synthesized by heating a mixture of Os<sub>3</sub>(CO)<sub>12</sub> and 3,5-dimethylpyrazole (Me<sub>2</sub>PzH) with microwave radiation. Two trinuclear complexes and a fourth dinuclear complex are also produced. Dimethylpyrazolato (Me<sub>2</sub>Pz<sup>–</sup>) ligands bridge two Os atoms in each complex. The trinuclear products Os<sub>3</sub>(μ-H)(μ-Me<sub>2</sub>Pz)(CO)<sub>10</sub> (<strong>1</strong>) and Os<sub>3</sub>(μ-H)<sub>2</sub>(μ-Me<sub>2</sub>Pz)<sub>2</sub>(CO)<sub>8</sub> (<strong>2</strong>) are produced by oxidative addition to Os<sub>3</sub>(CO)<sub>12</sub> of one and two equivalents of Me<sub>2</sub>PzH, respectively. The dinuclear product Os<sub>2</sub>(μ-Me<sub>2</sub>Pz)<sub>2</sub>(CO)<sub>6</sub> (<strong>3</strong>), a sawhorse complex that was the intended target of the reaction, is isolated in low yield. The dinuclear dihydride products are Os<sub>2</sub>(μ-H)(μ-Me<sub>2</sub>Pz)<sub>2</sub>(H)(CO)<sub>5</sub> (<strong>4</strong>) and two isomers of Os<sub>2</sub>(μ-H)(μ-Me<sub>2</sub>Pz)<sub>2</sub>(H)(CO)<sub>4</sub>(Me<sub>2</sub>PzH), one of which (<strong>5a</strong>) has a Me<sub>2</sub>PzH ligand <em>trans</em> to the bridging hydride and the other of which (<strong>5b</strong>) has a Me<sub>2</sub>PzH ligand <em>trans</em> to an N atom of one of the pyrazolato ligands. Complex <strong>5a</strong> is the major product. The Os<sub>2</sub> dihydrides represent a new class of diosmium carbonyl complexes. All products were structurally characterized by SC-XRD.<span><span>*</span></span></div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1048 ","pages":"Article 124032"},"PeriodicalIF":2.1,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146171223","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.2026.124029
Alaa Maatouk, Thibaud Rossel, Bruno Therrien
Selective recognition of biomolecules is of paramount importance in medicine, biotechnology, and cellular biology. Adenosine triphosphate (ATP), the universal energy currency of living systems, represents a valuable analytical target in sensing technology. However, discriminating ATP from its closely related analogues (ADP, AMP) remains a challenge. Herein, we report the synthesis of two arene ruthenium metalla-rectangles incorporating urea-based units. These water-stable assemblies are obtained from the dinuclear complex [Ru2(p-cymene)2{bis(2-hydroxyethyl)oxamidate}Cl2] and the bipyridyl connectors 1,1′-(1,4-phenylene)bis{3-(pyridin-4-yl)urea} (PPU) and 1,1′-(naphthalene-1,5-diyl)bis{3-(pyridin-4-yl)urea} (NPU) in the presence of silver triflate. Both metalla-rectangles are isolated as triflate salts, with the formula [Ru4(p-cymene)4{bis(2-hydroxyethyl)oxamidate}2(PPU)2](CF3SO3)4 (MRPPU) and [Ru4(p-cymene)4{bis(2-hydroxyethyl)ethanediamide}2(NPU)2](CF3SO3)4 (MRNPU), respectively. Both metalla-rectangles can interact with fluorescein (FLU) to form weakly-fluorescent host-guest systems, resulting in discrete fluorescent indicator displacement assays (FIDA). The MRPPU rectangle shows in buffered aqueous solution a selective ATP recognition over purine nucleotides, as opposed to MRNPU, with an affinity of 2.4 × 104 M-1 and a detection limit of 22.0 μM. The dissimilar response of these two metalla-rectangles is rationalized from their molecular design, suggesting distinct binding interactions with ATP.
{"title":"Selective recognition of ATP over phosphorylated molecules in aqueous media by urea-based arene ruthenium metalla-rectangle","authors":"Alaa Maatouk, Thibaud Rossel, Bruno Therrien","doi":"10.1016/j.jorganchem.2026.124029","DOIUrl":"10.1016/j.jorganchem.2026.124029","url":null,"abstract":"<div><div>Selective recognition of biomolecules is of paramount importance in medicine, biotechnology, and cellular biology. Adenosine triphosphate (ATP), the universal energy currency of living systems, represents a valuable analytical target in sensing technology. However, discriminating ATP from its closely related analogues (ADP, AMP) remains a challenge. Herein, we report the synthesis of two arene ruthenium metalla-rectangles incorporating urea-based units. These water-stable assemblies are obtained from the dinuclear complex [Ru<sub>2</sub>(<em>p</em>-cymene)<sub>2</sub>{bis(2-hydroxyethyl)oxamidate}Cl<sub>2</sub>] and the bipyridyl connectors 1,1′-(1,4-phenylene)bis{3-(pyridin-4-yl)urea} (PPU) and 1,1′-(naphthalene-1,5-diyl)bis{3-(pyridin-4-yl)urea} (NPU) in the presence of silver triflate. Both metalla-rectangles are isolated as triflate salts, with the formula [Ru<sub>4</sub>(<em>p</em>-cymene)<sub>4</sub>{bis(2-hydroxyethyl)oxamidate}<sub>2</sub>(PPU)<sub>2</sub>](CF<sub>3</sub>SO<sub>3</sub>)<sub>4</sub> (MRPPU) and [Ru<sub>4</sub>(<em>p</em>-cymene)<sub>4</sub>{bis(2-hydroxyethyl)ethanediamide}<sub>2</sub>(NPU)<sub>2</sub>](CF<sub>3</sub>SO<sub>3</sub>)<sub>4</sub> (MRNPU), respectively. Both metalla-rectangles can interact with fluorescein (FLU) to form weakly-fluorescent host-guest systems, resulting in discrete fluorescent indicator displacement assays (FIDA). The MRPPU rectangle shows in buffered aqueous solution a selective ATP recognition over purine nucleotides, as opposed to MRNPU, with an affinity of 2.4 × 10<sup>4</sup> M<sup>-1</sup> and a detection limit of 22.0 μM. The dissimilar response of these two metalla-rectangles is rationalized from their molecular design, suggesting distinct binding interactions with ATP.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1048 ","pages":"Article 124029"},"PeriodicalIF":2.1,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146037032","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}
Halogen atom transfer (XAT) reactions are fundamental in radical-mediated organic synthesis, visible-light photocatalysis, and electro-organic transformations. Accurate prediction of activation barriers is essential to mechanistic understanding and rational design of novel radical pathways. Herein, we present a systematic benchmark of 24 density functional theory (DFT) methods — including GGA, hybrid GGA, (hybrid) meta-GGA, and double-hybrid functionals — against high-level DLPNO-CCSD(T)/CBS reference energies for a diverse set of 15 representative XAT reactions involving various halogens (Cl, Br, I) and radical types. Based on our benchmarking results, we propose CAM-B3LYP-D3(BJ) as a reliable computational protocol for main-group XAT reactions in future mechanistic studies.
{"title":"Benchmarking of density functional theory calculation approaches for activation barriers in halogen atom transfer reactions","authors":"Tianyi Chen , Chaoyue Zhao , Shuoqing Zhang , Xin Hong","doi":"10.1016/j.jorganchem.2026.124013","DOIUrl":"10.1016/j.jorganchem.2026.124013","url":null,"abstract":"<div><div>Halogen atom transfer (XAT) reactions are fundamental in radical-mediated organic synthesis, visible-light photocatalysis, and electro-organic transformations. Accurate prediction of activation barriers is essential to mechanistic understanding and rational design of novel radical pathways. Herein, we present a systematic benchmark of 24 density functional theory (DFT) methods — including GGA, hybrid GGA, (hybrid) meta-GGA, and double-hybrid functionals — against high-level DLPNO-CCSD(T)/CBS reference energies for a diverse set of 15 representative XAT reactions involving various halogens (Cl, Br, I) and radical types. Based on our benchmarking results, we propose CAM-B3LYP-D3(BJ) as a reliable computational protocol for main-group XAT reactions in future mechanistic studies.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1048 ","pages":"Article 124013"},"PeriodicalIF":2.1,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076440","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: 2026-01-23DOI: 10.1016/j.jorganchem.2026.124033
Yingqiao Wang , Ruitao Feng , Yilan Jin , Hong Yang , Xu Chen
α-Octabutoxy-naphthalocyanine palladium(II), denoted as PdNc(OBu)8, has been successfully synthesized. To improve water solubility and biocompatibility, we encapsulated it with bovine serum albumin (BSA) to form nanoparticles of PdNc(OBu)8 NPs. The nanoparticles show strong NIR absorption centered at 825 nm. Under 808 nm laser irradiation, PdNc(OBu)8 NPs generate both singlet oxygen (1O2) and superoxide radical (O2•−). They also act as strong photothermal agents with a photothermal conversion efficiency of ∼66%. For 4T1 cells, the NIR irradiation of PdNc(OBu)8 NPs causes marked cell death with the photothermal and type I/II photodynamic effect. All these results supported PdNc(OBu)8 NPs should be promising for combined type I/II photodynamic and photothermal cancer therapy.
{"title":"NIR-activated α-Octabutoxy-naphthalocyanine palladium(II) nanoparticles for synergistic photothermal and type Ι/II photodynamic therapy of cancer cells","authors":"Yingqiao Wang , Ruitao Feng , Yilan Jin , Hong Yang , Xu Chen","doi":"10.1016/j.jorganchem.2026.124033","DOIUrl":"10.1016/j.jorganchem.2026.124033","url":null,"abstract":"<div><div>α-Octabutoxy-naphthalocyanine palladium(II), denoted as PdNc(OBu)<sub>8</sub>, has been successfully synthesized. To improve water solubility and biocompatibility, we encapsulated it with bovine serum albumin (BSA) to form nanoparticles of PdNc(OBu)<sub>8</sub> NPs. The nanoparticles show strong NIR absorption centered at 825 nm. Under 808 nm laser irradiation, PdNc(OBu)<sub>8</sub> NPs generate both singlet oxygen (<sup>1</sup>O<sub>2</sub>) and superoxide radical (O<sub>2</sub><sup>•−</sup>). They also act as strong photothermal agents with a photothermal conversion efficiency of ∼66%. For 4T1 cells, the NIR irradiation of PdNc(OBu)<sub>8</sub> NPs causes marked cell death with the photothermal and type I/II photodynamic effect. All these results supported PdNc(OBu)<sub>8</sub> NPs should be promising for combined type I/II photodynamic and photothermal cancer therapy.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1048 ","pages":"Article 124033"},"PeriodicalIF":2.1,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076449","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 migration of small-molecule burning rate catalysts (BRCs) remains a critical bottleneck limiting the stability and shelf-life of composite solid propellants. To overcome this challenge without compromising catalytic efficiency, we report a facile ionic self-assembly strategy to construct a new class of polynuclear ferrocenyl-carboxylate complexes. By electrostatically coupling (ferrocenylmethyl)trimethylammonium cations with carboxylate anions of varying valency (acetate, oxalate, citrate, and EDTA), four distinct ionic catalysts (IFC-1 to IFC-4) were synthesized. Among these, the tetranuclear complex IFC-4 exhibited the most promising properties. Electrochemical analysis revealed that IFC-4 possesses a unique redox behavior with a high oxidation potential (0.81 V), contributing to its stability. When applied to ammonium perchlorate (AP), IFC-4 (5 wt%) demonstrated superior catalytic activity, reducing the high-temperature decomposition peak by 79 °C and increasing the decomposition rate constant by 12-fold compared to pure AP. Crucially, accelerated aging tests confirmed that IFC-4 exhibits exceptional anti-migration performance, with a diffusion coefficient of 8.70 × 10⁻¹¹ cm² s⁻¹—approximately two orders of magnitude lower than that of commercial catocene (2.38 × 10⁻⁹ cm² s⁻¹). This drastic reduction in mobility is attributed to the synergistic effects of increased molecular weight, structural rigidity, and strong electrostatic anchoring within the propellant binder network. These findings establish ionic self-assembly as a robust pathway for engineering high-performance, migration-resistant energetic catalysts.
{"title":"Tunable ionic self-assembly of Ferrocenyl-Carboxylate complexes: A new class of anti-migration burning rate catalysts for ammonium perchlorate-based propellants","authors":"Qun Luo, Xueyi Chang, Xuexuan Luo, Zhiyu Cheng, Yongfu Qiu, Guiping Tan, Muqing Chen","doi":"10.1016/j.jorganchem.2026.124057","DOIUrl":"10.1016/j.jorganchem.2026.124057","url":null,"abstract":"<div><div>The migration of small-molecule burning rate catalysts (BRCs) remains a critical bottleneck limiting the stability and shelf-life of composite solid propellants. To overcome this challenge without compromising catalytic efficiency, we report a facile ionic self-assembly strategy to construct a new class of polynuclear ferrocenyl-carboxylate complexes. By electrostatically coupling (ferrocenylmethyl)trimethylammonium cations with carboxylate anions of varying valency (acetate, oxalate, citrate, and EDTA), four distinct ionic catalysts (IFC-1 to IFC-4) were synthesized. Among these, the tetranuclear complex IFC-4 exhibited the most promising properties. Electrochemical analysis revealed that IFC-4 possesses a unique redox behavior with a high oxidation potential (0.81 V), contributing to its stability. When applied to ammonium perchlorate (AP), IFC-4 (5 wt%) demonstrated superior catalytic activity, reducing the high-temperature decomposition peak by 79 °C and increasing the decomposition rate constant by 12-fold compared to pure AP. Crucially, accelerated aging tests confirmed that IFC-4 exhibits exceptional anti-migration performance, with a diffusion coefficient of 8.70 × 10⁻¹¹ cm² s⁻¹—approximately two orders of magnitude lower than that of commercial catocene (2.38 × 10⁻⁹ cm² s⁻¹). This drastic reduction in mobility is attributed to the synergistic effects of increased molecular weight, structural rigidity, and strong electrostatic anchoring within the propellant binder network. These findings establish ionic self-assembly as a robust pathway for engineering high-performance, migration-resistant energetic catalysts.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1048 ","pages":"Article 124057"},"PeriodicalIF":2.1,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146171219","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: 2026-01-30DOI: 10.1016/j.jorganchem.2026.124049
Abdelhak Lachguar , Shagun Chhetri , Ahmad Joumaa , Jean-Claude Daran , Rinaldo Poli , Eric Manoury , Eric Deydier
Racemic and chiral P,S ferrocenyl ligands bearing a phenol function for further catalyst grafting were synthesized and fully characterized (multinuclear NMR, high-resolution MS, X-ray diffraction). Analogs bearing a methoxy group instead of OH (anisole instead of phenol) were also synthesized to mimic the expected ether formation after grafting in order to assess the ether group influence on catalysis. Good activity and enantioselectivity (up to 78%), similar to non-functionalized ligands, were obtained in the asymmetric hydrogenation of acetophenone. The base concentration appears to have major influence on both activity and enantioselectivity.
{"title":"Synthesis of chiral P,S ferrocenyl ligands for catalyst heterogenization and testing in the homogeneous asymmetric hydrogenation of acetophenone","authors":"Abdelhak Lachguar , Shagun Chhetri , Ahmad Joumaa , Jean-Claude Daran , Rinaldo Poli , Eric Manoury , Eric Deydier","doi":"10.1016/j.jorganchem.2026.124049","DOIUrl":"10.1016/j.jorganchem.2026.124049","url":null,"abstract":"<div><div>Racemic and chiral P,S ferrocenyl ligands bearing a phenol function for further catalyst grafting were synthesized and fully characterized (multinuclear NMR, high-resolution MS, X-ray diffraction). Analogs bearing a methoxy group instead of OH (anisole instead of phenol) were also synthesized to mimic the expected ether formation after grafting in order to assess the ether group influence on catalysis. Good activity and enantioselectivity (up to 78%), similar to non-functionalized ligands, were obtained in the asymmetric hydrogenation of acetophenone. The base concentration appears to have major influence on both activity and enantioselectivity.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1048 ","pages":"Article 124049"},"PeriodicalIF":2.1,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146171218","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: 2026-01-30DOI: 10.1016/j.jorganchem.2026.124052
Ahmed B.M. Ibrahim , Waqar Uddin , Ayesha Aftab , Mohamed A. Habib , Fawad Ahmad , Mudassir Iqbal , Khalid I. Anojaidi , Waleed A. Al-Suwaylih
The increasing need for environmentally sustainable and efficient energy storage technologies has intensified interest in alternative electrode materials that can overcome the inherent limitations of conventional inorganic systems. Organometallic compounds (OMCs) have gained considerable attention due to their ability to combine tunable organic architectures with electrochemically active metal centers. This review provides a comprehensive assessment of the structural configurations of OMCs, spanning from molecular complexes to extended frameworks such as metal–organic frameworks, and discusses their electrochemical charge storage behavior influenced by ligand modification and metal-based redox processes. The performance of OMC-based electrodes is evaluated across a range of energy storage platforms, including rechargeable batteries, multivalent ion systems, redox flow batteries, and supercapacitors. Key challenges, particularly those related to electronic conductivity and durability during long-term cycling, are critically analyzed. Finally, future research opportunities are outlined to guide the development of optimized OMC-based materials for high energy density, adaptable, and sustainable energy storage applications.
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