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Reactivity studies of saccharin at a diphosphine-stabilized low-valent triruthenium center to show a new, simple but elusive coordination mode of saccharinate ligand 糖精在二膦稳定的低价三钌中心的反应性研究,揭示了一种新的、简单但难以捉摸的糖化配体配位模式
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-02-15 Epub Date: 2025-12-25 DOI: 10.1016/j.jorganchem.2025.123994
Jannatul F. Raka , Nahid Akter , Md. Mahbub Alam , Subas Rajbangshi , Vladimir N. Nesterov , Shariff E. Kabir , Shishir Ghosh
The reactivity of saccharin (sacH) towards the diphosphine-stabilized triruthenium [Ru3(CO)10(μ-dppm)] has been investigated. Thus, the reaction between [Ru3(CO)10(μ-dppm)] and sacH in refluxing benzene leads to the formation of [Ru3(CO)8(μ-dppm)(μ-H)(μ-sac)] (1) and [Ru2(CO)4(μ-dppm)(μ-sac)2] (2), with the triruthenium 1 being isolated as the major product. The sac ligand displays the typical edge-bridging coordination mode using nitrogen and the amide oxygen atoms in both 1 and 2. Oxidative decarbonylation of 1 using Me3NO in the presence of PPh3 affords simple phosphine-substituted product, [Ru3(CO)7(μ-dppm)(μ-H)(PPh3)(μ-sac)] (3), at room temperature which converts into [Ru3(CO)4(μ-H)(μ3-H)(η1-Ph)(μ-PPh2){μ-Ph2PCH2P(Ph)C6H4}(μ3-sac)] (4) upon thermolysis in refluxing toluene. The coordination mode of the sac ligand changes from edge-bridging to triply-bridging/face-capping during the conversion process. The triply-bridging coordination mode of the sac ligand observed in 4, where it bridges a metal-metal edge using the nitrogen atom and coordinates with a third metal atom through the amide oxygen atom, is novel. Compound 2 also reacts with PR3 (R = Ph, OMe) at room temperature to yield simple phosphine-substituted product, [Ru2(CO)3(μ-dppm)(PR3)(μ-sac)2] (5, R = Ph; 6, R = OMe), however, “flipping” of one of the coordinated sac ligand is also observed during this substitution reaction. Several control experiments have been conducted to investigate the relationship between the products and to discuss the mechanisms involved in the formation of 1-6. The molecular structures of 1-4 and 6 have been determined by X-ray crystallography.
研究了糖精(sacH)对二膦稳定的三钌Ru3(CO)10(μ-dppm)的反应性。在回流苯中,[Ru3(CO)10(μ-dppm)]与sacH反应生成[Ru3(CO)8(μ-dppm)(μ-H)(μ-sac)](1)和[Ru2(CO)4(μ-dppm)(μ-sac)2](2),主要产物为三钌1。囊配体表现出典型的边桥配位模式,在1和2中均使用氮和酰胺氧原子。在PPh3存在下,Me3NO对1进行氧化脱羰反应,得到简单的膦取代产物[Ru3(CO)7(μ-dppm)(μ-H)(PPh3)(μ-sac)](3),在室温下,在回流甲苯中进行热裂解,转化为[Ru3(CO)4(μ-H)(μ-H)(η -Ph)(μ-PPh2){μ-Ph2PCH2P(Ph)C6H4}(μ-sac)](4)。在转化过程中,囊配体的配位方式由边桥式转变为三桥式/面盖式。在4中观察到的囊配体的三桥接配位模式是新颖的,它使用氮原子桥接金属-金属边缘,并通过酰胺氧原子与第三个金属原子配位。化合物2也与PR3 (R = Ph, OMe)在室温下反应生成简单的膦取代产物[Ru2(CO)3(μ-dppm)(PR3)(μ-sac)2] (5, R = Ph; 6, R = OMe),但在此取代反应中也观察到其中一个配位囊配体的“翻转”。几个对照实验已经进行了调查产品之间的关系,并讨论了机制参与形成1-6。用x射线晶体学测定了1-4和6的分子结构。
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引用次数: 0
An overview of palladium nanocatalysts anchored on carbon nanotubes for nitroarene reduction 碳纳米管上钯纳米催化剂用于硝基芳烃还原的综述
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-02-15 Epub Date: 2025-12-22 DOI: 10.1016/j.jorganchem.2025.123989
Sara Payamifar, Ahmad Poursattar Marjani
Nitroarenes and organic dyes are recalcitrant contaminants that typically occur in wastewater generated by industrial processes. They are poisonous to sea organisms; therefore, their expulsion from underwater systems is valuable. Systems according to palladium nanoparticles (Pd NPs) supported on carbon nanotubes (CNTs) are more efficient than traditional systems. This study comprehensively outlines recent advances in the synthesis, characterization, and catalytic applications of Pd NPs supported on CNTs for the selective reduction of nitroarenes. Emphasis is placed on the unique physicochemical properties of CNTs that enhance Pd dispersion, stability, and catalytic efficiency. The review highlights the catalytic performance of these nanocatalysts under mild and environmentally benign conditions, focusing on reaction mechanisms, substrate scope, and recyclability. Challenges such as catalyst deactivation and scale-up potential are addressed, along with prospects for future development in green catalytic processes leveraging CNT-supported Pd systems for sustainable organic transformations.
硝基芳烃和有机染料是顽固性污染物,通常出现在工业过程产生的废水中。它们对海洋生物有毒;因此,将它们驱逐出水下系统是有价值的。基于碳纳米管(CNTs)的钯纳米颗粒(Pd NPs)系统比传统系统效率更高。本研究全面概述了碳纳米管负载Pd NPs在硝基芳烃选择性还原中的合成、表征和催化应用方面的最新进展。重点放在碳纳米管的独特的物理化学性质,提高Pd分散,稳定性和催化效率。本文重点介绍了这些纳米催化剂在温和和环境友好条件下的催化性能,重点介绍了反应机理、底物范围和可回收性。解决了催化剂失活和放大潜力等挑战,以及利用碳纳米管支持的Pd系统实现可持续有机转化的绿色催化过程的未来发展前景。
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引用次数: 0
Competition between water and a bulky isocyanide in Pd(II) complexes with auxiliary 1,1′-bis(diphenylphosphino)ferrocene ligand 与辅助性1,1 ' -二苯基膦二茂铁配体的Pd(II)配合物中水和大体积异氰化物之间的竞争
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-02-15 Epub Date: 2025-12-16 DOI: 10.1016/j.jorganchem.2025.123985
Ondřej Bárta, Ivana Císařová, Petr Štěpnička
The reaction of the dimeric Pd(II)-dppf complex [Pd2(μ-Cl)2(dppf-κ2P,P′)2][BF4]2 (1; dppf = 1,1′-bis(diphenylphosphino)ferrocene) with isocyanide XylNC (Xyl = 2,6-dimethylphenyl) proceeds under the cleavage of the chloride bridges to produce the isocyanide complex [PdCl(dppf-κ2P,P′)(XylNC-κC)][BF4] (3). The subsequent removal of the Pd-bound chloride with Ag[BF4] converts compound 3 into a mixture of the bis(isocyanide) complex [Pd(dppf-κ2P,P′)(XylNC-κC)2][BF4]2 (5) and the diaqua complex [Pd(dppf-κ2P,P′)(H2O)2][BF4]2 (4). Both compounds can be selectively obtained from 1 under modified reaction conditions. Complex 4 readily condenses into a hydroxide-bridged dimer [Pd2(μ-OH)2(dppf-κ2P,P′)2][BF4]2 (6) and can be converted to 1 and [PdCl2(dppf-κ2P,P′)] (2) (via reactions with a Cl source) or 5 (via reaction with XylNC). The facile dissociation of the XylNC ligand was explained by the antisymbiosis of the soft phosphine and isocyanide ligands.
二聚体Pd(II)-dppf配合物[Pd2(μ-Cl)2(dppf-κ2P,P′)2][BF4]2 (1; dppf = 1,1′-双(二苯基膦)二茂铁)与异氰化物XylNC (Xyl = 2,6-二甲基苯基)在氯桥断裂下反应生成异氰化物配合物[PdCl(dppf-κ2P,P′)(XylNC-κC)][BF4](3)。随后用Ag[BF4]去除Pd结合的氯化物,将化合物3转化为双(异氰化物)络合物[Pd(dppf-κ2P,P ')(XylNC-κC)2][BF4]2(5)和双水络合物[Pd(dppf-κ2P,P ')(H2O)2][BF4]2(4)的混合物。在改进的反应条件下,这两种化合物都可以选择性地从1中得到。配合物4易于缩合成羟基桥接二聚体[Pd2(μ-OH)2(dppf-κ2P,P′)2][BF4]2(6),并可通过与Cl−源反应转化为1和[PdCl2(dppf-κ2P,P′)](2)或通过与XylNC反应转化为5。XylNC配体的易解离可以用软膦和异氰化物配体的抗共生来解释。
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引用次数: 0
A decade of progress in direct C–H selenation: A modern strategy for C–Se bond formation C-H直接硒化的十年进展:C-Se键形成的现代策略
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-02-15 Epub Date: 2025-12-20 DOI: 10.1016/j.jorganchem.2025.123987
Ghada Al-Assi , Ahmed M. Amshawee , Subbulakshmi Ganesan , Shaker Al-Hasnaawei , Radwan Ali , C.P. Surya , Renu Sharma , Aashna Sinha , Mosstafa Kazemi
Organoselenium compounds have attracted growing attention due to their diverse applications in medicinal chemistry, agrochemicals, catalysis, and materials science. As a result, the development of efficient and sustainable methodologies for constructing carbon–selenium (C–Se) bonds has become a vibrant area of research. Conventional strategies, including nucleophilic substitution, electrophilic selenation, and transition-metal–catalyzed cross-coupling, though powerful, typically require prefunctionalized substrates, multiple steps, and generate undesirable waste. In the last decade, direct C–H selenation has emerged as a modern and transformative approach that enables the direct conversion of inert C–H bonds into C–Se bonds without preactivation. This strategy embodies step and atom economy, provides access to structurally diverse selenium-containing frameworks, and offers unique opportunities for late-stage functionalization of bioactive molecules and complex scaffolds. Advances in transition-metal catalysis, photocatalysis, and electrochemical activation have expanded the scope of C–H selenation to arenes, heteroarenes, alkenes, and even alkanes under increasingly mild and sustainable conditions. This review highlights the significant progress achieved in the past decade, discussing catalytic systems, mechanistic insights, substrate scope, and prospects of C–H selenation as a cutting-edge methodology for C–Se bond construction.
有机硒化合物因其在药物化学、农用化学、催化和材料科学等方面的广泛应用而受到越来越多的关注。因此,开发高效和可持续的碳硒(C-Se)键构建方法已成为一个充满活力的研究领域。传统的策略,包括亲核取代,亲电硒化和过渡金属催化的交叉偶联,虽然强大,但通常需要预功能化底物,多个步骤,并产生不希望的浪费。在过去的十年中,直接碳氢硒化已经成为一种现代的、革命性的方法,它使惰性碳氢键直接转化为碳硒键而无需预活化。该策略体现了步骤经济和原子经济,提供了结构多样化的含硒框架,并为生物活性分子和复杂支架的后期功能化提供了独特的机会。过渡金属催化、光催化和电化学活化的进展使碳氢硒化反应的范围扩大到芳烃、杂芳烃、烯烃甚至烷烃,其反应条件越来越温和和可持续。本文综述了在过去十年中取得的重大进展,讨论了催化体系、机制见解、底物范围以及C-H硒化作为C-Se键构建的前沿方法的前景。
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引用次数: 0
Construction of MWCNTs/MNPs-based copper nanocomposite as an efficient and reusable catalyst for four-component preparation of highly substituted pyridines MWCNTs/ mnps基铜纳米复合材料高效可重复使用的四组分高取代吡啶制备催化剂的构建
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-02-15 Epub Date: 2026-01-03 DOI: 10.1016/j.jorganchem.2026.124011
Mohamed Abu Shuheil , Ahmed Aldulaimi , Rekha MM , Subhashree Ray , Omayma Salim Waleed , CP. Surya , Renu Sharma , Vatsal Jain
A sustainable and highly efficient four-component protocol has been established for the synthesis of structurally diverse and highly substituted pyridine derivatives. The catalytic system, MWCNTs/MNPs–Tris(2-aminoethyl)amine–CuCl₂, effectively promotes the one-pot condensation of aromatic aldehydes, malononitrile, ethyl acetoacetate, and substituted anilines in aqueous medium under reflux conditions. This green catalytic method provides the desired pyridines in excellent yields (86–98%) within 1 h, highlighting its remarkable activity and selectivity. The reaction system exhibits wide substrate compatibility, tolerating both electron-donating and electron-withdrawing substituents on the aromatic rings. Product identity and purity were confirmed by melting-point determination and observation of crystalline or oily characteristics. A comparative evaluation with existing protocols demonstrates significant advantages in yield, environmental compatibility, and operational simplicity. The use of water as an environmentally benign solvent, along with the recyclable magnetic nanocatalyst, underscores the method's sustainability and reusability. Overall, this approach provides a green, rapid, and practical route to valuable pyridine-based heterocycles with potential biological relevance.
建立了一种可持续、高效的四组分方案,用于合成结构多样、高取代的吡啶衍生物。MWCNTs/ MNPs-Tris(2-氨基乙基)胺- cucl₂催化体系在回流条件下可有效促进芳香醛、丙二腈、乙酰乙酸乙酯和取代苯胺在水介质中的一锅缩合反应。该绿色催化方法在1 h内以86-98%的收率获得了理想的吡啶,突出了其良好的活性和选择性。该反应体系具有广泛的底物相容性,可耐受芳香环上的供电子和吸电子取代基。通过熔点测定和观察结晶或油性特征来确定产品的纯度。与现有方案的比较评估表明,在产量、环境兼容性和操作简单性方面具有显着优势。使用水作为环保溶剂,以及可回收的磁性纳米催化剂,强调了该方法的可持续性和可重复使用性。总的来说,这种方法提供了一条绿色、快速和实用的途径,可以获得具有潜在生物学意义的有价值的吡啶类杂环化合物。
{"title":"Construction of MWCNTs/MNPs-based copper nanocomposite as an efficient and reusable catalyst for four-component preparation of highly substituted pyridines","authors":"Mohamed Abu Shuheil ,&nbsp;Ahmed Aldulaimi ,&nbsp;Rekha MM ,&nbsp;Subhashree Ray ,&nbsp;Omayma Salim Waleed ,&nbsp;CP. Surya ,&nbsp;Renu Sharma ,&nbsp;Vatsal Jain","doi":"10.1016/j.jorganchem.2026.124011","DOIUrl":"10.1016/j.jorganchem.2026.124011","url":null,"abstract":"<div><div>A sustainable and highly efficient four-component protocol has been established for the synthesis of structurally diverse and highly substituted pyridine derivatives. The catalytic system, MWCNTs/MNPs–Tris(2-aminoethyl)amine–CuCl₂, effectively promotes the one-pot condensation of aromatic aldehydes, malononitrile, ethyl acetoacetate, and substituted anilines in aqueous medium under reflux conditions. This green catalytic method provides the desired pyridines in excellent yields (86–98%) within 1 h, highlighting its remarkable activity and selectivity. The reaction system exhibits wide substrate compatibility, tolerating both electron-donating and electron-withdrawing substituents on the aromatic rings. Product identity and purity were confirmed by melting-point determination and observation of crystalline or oily characteristics. A comparative evaluation with existing protocols demonstrates significant advantages in yield, environmental compatibility, and operational simplicity. The use of water as an environmentally benign solvent, along with the recyclable magnetic nanocatalyst, underscores the method's sustainability and reusability. Overall, this approach provides a green, rapid, and practical route to valuable pyridine-based heterocycles with potential biological relevance.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1046 ","pages":"Article 124011"},"PeriodicalIF":2.1,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922195","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}
引用次数: 0
Cycloaddition of CO2 with epoxides into cyclic carbonates catalyzed by cobalt(II or II/III)-arylhydrazonates 钴(II或II/III)-芳酰腙催化CO2与环氧化物环加成成环状碳酸盐
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-02-15 Epub Date: 2025-10-21 DOI: 10.1016/j.jorganchem.2025.123901
Tahir A. Javadzade , Sevinc R. Hajiyeva , Famil M. Chyragov , Ana V.M. Nunes , Jamal Lasri , Sahil Z. Hamidov , Khudayar I. Hasanov , Kamran T. Mahmudov
A series of known cobalt complexes, [Co(HL1)2(H2O)4]·2H2O (1) (HL1 = 4-(2-(2,4-dioxopentan-3-ylidene)hydrazineyl)benzoate), [Co(μ-HL2)(H2O)(DMF)]2·DMF (2) (HL2 = (Z)-1-(2-carboxylatophenyl)-2-(1-cyano-2-imino-2-methoxyethylidene)hydrazin-1-ide), [CoII(H2O)2(DMF)2{CoIII(HL3)2}2]·2H2O (3) (HL3 = (Z)-1-(2-carboxylatophenyl)-2-(1,3-dioxo-1-(phenylamino)butan-2-ylidene)hydrazin-1-ide), [CoII(μ-HL3)(MeOH)2]n (4) and [CoII(H2O)4{CoIII(HL4)2}2]·12H2O (5) (HL4 = 1-(2-carboxylatophenyl)-2-(4,4-dimethyl-2,6-dioxocyclohexylidene)hydrazin-1-ide), were synthesized and applied as catalysts in the coupling of CO2 with epoxides in the presence and absence of tetrabutylammonium chloride (TBACl), tetrabutylammonium bromide (TBABr), and tetrabutylammonium iodide (TBAI). Dependent on the nature of the starting epoxide, moderate to good yields (ranging from 31 to 74 %) of the cyclic carbonates were achieved in the reactions catalyzed by 3 under appropriate conditions (24 h, 60 °C and 40 bar pressure).
已知的一系列钴配合物,[Co(HL1)2(H2O)4]·2H2O (1) (HL1 = 4-(2-(2,4-二氧基-3-酰基)肼基)苯甲酸酯),[Co(μ-HL2)(H2O)(DMF)]2·DMF (2) (HL2 = (Z)-1-(2-羧基-2-亚胺-2-甲氧基乙基)肼基),[CoII(H2O)2(DMF)2{CoIII(HL3)2}2]·2H2O (3) (HL3 = (Z)-1-(2-羧基- latophenyl)-2-(1,3-二氧基-1-(苯基氨基)丁基-2-酰基)肼基),合成了[CoII(μ-HL3)(MeOH)2]n(4)和[CoII(H2O)4{CoIII(HL4)2}2]·12H2O (5) (HL4 = 1-(2-羧基苯基)-2-(4,4-二甲基-2,6-二氧环己基)肼-1-ide),并在四丁基氯化铵(TBACl)、四丁基溴化铵(TBABr)和四丁基碘化铵(TBAI)存在和不存在的情况下作为催化剂用于CO2与环氧化物的偶联反应。根据起始环氧化物的性质,在适当的条件下(24小时,60℃,40 bar压力),由3催化的反应中,环状碳酸盐的收率为中等至良好(31%至74%)。
{"title":"Cycloaddition of CO2 with epoxides into cyclic carbonates catalyzed by cobalt(II or II/III)-arylhydrazonates","authors":"Tahir A. Javadzade ,&nbsp;Sevinc R. Hajiyeva ,&nbsp;Famil M. Chyragov ,&nbsp;Ana V.M. Nunes ,&nbsp;Jamal Lasri ,&nbsp;Sahil Z. Hamidov ,&nbsp;Khudayar I. Hasanov ,&nbsp;Kamran T. Mahmudov","doi":"10.1016/j.jorganchem.2025.123901","DOIUrl":"10.1016/j.jorganchem.2025.123901","url":null,"abstract":"<div><div>A series of known cobalt complexes, [Co(HL<sup>1</sup>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]·2H<sub>2</sub>O (<strong>1</strong>) (HL<sup>1</sup> = 4-(2-(2,4-dioxopentan-3-ylidene)hydrazineyl)benzoate), [Co(<em>μ</em>-HL<sup>2</sup>)(H<sub>2</sub>O)(DMF)]<sub>2</sub>·DMF (<strong>2</strong>) (HL<sup>2</sup> = (<em>Z</em>)-1-(2-carboxylatophenyl)-2-(1-cyano-2-imino-2-methoxyethylidene)hydrazin-1-ide), [Co<sup>II</sup>(H<sub>2</sub>O)<sub>2</sub>(DMF)<sub>2</sub>{Co<sup>III</sup>(HL<sup>3</sup>)<sub>2</sub>}<sub>2</sub>]·2H<sub>2</sub>O (<strong>3</strong>) (HL<sup>3</sup> = (<em>Z</em>)-1-(2-carboxylatophenyl)-2-(1,3-dioxo-1-(phenylamino)butan-2-ylidene)hydrazin-1-ide), [Co<sup>II</sup>(<em>μ</em>-HL<sup>3</sup>)(MeOH)<sub>2</sub>]<sub>n</sub> (<strong>4</strong>) and [Co<sup>II</sup>(H<sub>2</sub>O)<sub>4</sub>{Co<sup>III</sup>(HL<sup>4</sup>)<sub>2</sub>}<sub>2</sub>]·12H<sub>2</sub>O (<strong>5</strong>) (HL<sup>4</sup> = 1-(2-carboxylatophenyl)-2-(4,4-dimethyl-2,6-dioxocyclohexylidene)hydrazin-1-ide), were synthesized and applied as catalysts in the coupling of CO<sub>2</sub> with epoxides in the presence and absence of tetrabutylammonium chloride (TBACl), tetrabutylammonium bromide (TBABr), and tetrabutylammonium iodide (TBAI). Dependent on the nature of the starting epoxide, moderate to good yields (ranging from 31 to 74 %) of the cyclic carbonates were achieved in the reactions catalyzed by 3 under appropriate conditions (24 h, 60 °C and 40 bar pressure).</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1046 ","pages":"Article 123901"},"PeriodicalIF":2.1,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882088","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}
引用次数: 0
Self-assembly of half-sandwich iridium-based metallarectangles for the encapsulation of polycyclic aromatic hydrocarbons 半夹心铱基金属矩形的自组装封装多环芳烃
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-02-15 Epub Date: 2025-12-30 DOI: 10.1016/j.jorganchem.2025.123998
Si Nian , Zhi-Yang Chen , Shou-You Jiao , Ming-Xin Liang , Yu-Fei Zhu , Chengzhu He , Xianghuan Shan , Wei-Long Shan
The rational design and synthesis of metallarectangles with tailored cavities and functionalities remain a formidable challenge in organometallic supramolecular chemistry. Here, we report two half-sandwich iridium-based metallarectangles, [Cp₂Ir₂Cl₂]₂L₂(OTf)₄ (1) and [Cp₂Ir₂(μ-DHBQ)]₂L₂(OTf)₄ (2), which were obtained in high yields via coordination-driven self-assembly of binuclear precursors B1 and B2 employing a 2,1,3-benzothiadiazole (BTD)-based bidentate ligand L. Based on single-crystal XRD analysis, the molecular structures of these complexes adopt tetranuclear rectangular macrocyclic architectures with cavities of distinct dimensions. Subsequent NMR titration studies confirmed that metallarectangle 2 exhibits exceptional host-guest properties, notably encapsulating electron-rich polycyclic aromatic hydrocarbons (PAHs) such as anthracene, phenanthrene, and pyrene. Additionally, the crystal structure of complex 2⊃pyrene provides molecular-level insight into the key interactions governing host-guest assembly and stability.
在有机金属超分子化学中,合理设计和合成具有定制腔体和功能的金属矩形仍然是一个艰巨的挑战。本文报道了以2,1,3-苯并噻唑(BTD)为基础的双齿配体L,通过配位驱动自组装双核前体B1和B2,以高收率制备了[Cp₂Ir₂Cl₂]₂L₂(OTf)₄(1)和[Cp₂Ir₂(μ-DHBQ)]₂L₂(OTf)₄(2)两种半夹心铱基金属矩形配合物。随后的核磁共振滴定研究证实,金属矩形2表现出特殊的主客体性质,特别是封装富电子的多环芳烃(PAHs),如蒽、菲和芘。此外,复合体2、芘的晶体结构提供了分子水平上对主客体组装和稳定性的关键相互作用的洞察。
{"title":"Self-assembly of half-sandwich iridium-based metallarectangles for the encapsulation of polycyclic aromatic hydrocarbons","authors":"Si Nian ,&nbsp;Zhi-Yang Chen ,&nbsp;Shou-You Jiao ,&nbsp;Ming-Xin Liang ,&nbsp;Yu-Fei Zhu ,&nbsp;Chengzhu He ,&nbsp;Xianghuan Shan ,&nbsp;Wei-Long Shan","doi":"10.1016/j.jorganchem.2025.123998","DOIUrl":"10.1016/j.jorganchem.2025.123998","url":null,"abstract":"<div><div>The rational design and synthesis of metallarectangles with tailored cavities and functionalities remain a formidable challenge in organometallic supramolecular chemistry. Here, we report two half-sandwich iridium-based metallarectangles, [Cp₂Ir₂Cl₂]₂L₂(OTf)₄ (1) and [Cp₂Ir₂(<em>μ</em>-DHBQ)]₂L₂(OTf)₄ (2), which were obtained in high yields via coordination-driven self-assembly of binuclear precursors B1 and B2 employing a 2,1,3-benzothiadiazole (BTD)-based bidentate ligand L. Based on single-crystal XRD analysis, the molecular structures of these complexes adopt tetranuclear rectangular macrocyclic architectures with cavities of distinct dimensions. Subsequent NMR titration studies confirmed that metallarectangle 2 exhibits exceptional host-guest properties, notably encapsulating electron-rich polycyclic aromatic hydrocarbons (PAHs) such as anthracene, phenanthrene, and pyrene. Additionally, the crystal structure of complex 2⊃pyrene provides molecular-level insight into the key interactions governing host-guest assembly and stability.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1046 ","pages":"Article 123998"},"PeriodicalIF":2.1,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882164","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}
引用次数: 0
Biosynthesis of a recyclable MOF catalyst (UiO-66-NH2/Pd) mediated by Lavandula angustifolia extract: Investigation of its catalytic activity in Suzuki-Miyaura coupling reactions 薰衣草提取物介导的可循环MOF催化剂UiO-66-NH2/Pd的生物合成及其在Suzuki-Miyaura偶联反应中的催化活性研究
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-02-15 Epub Date: 2025-12-23 DOI: 10.1016/j.jorganchem.2025.123991
Narinderjit Singh Sawaran Singh , Rafid Kamal Jameel , Ahmed Aldulaimi , Malatesh Akkur , Satish Kumar Samal , Sridharan Sundharam , Sanjeev Kumar , Khalmurat Iliev , Zukhra Atamuratova , D. Yolchiev , Aseel Smerat , H. Amin El Sabban
This inclusive innovation research achieved the successful addition of palladium nanoparticles into the metal–organic framework material UiO-66-NH2, mediated by an aqueous extract of Lavandula angustifolia flower, as a natural reducing agent. Detailed analysis using various methods, such as TEM, FE-SEM, EDX, ICP-OES, and XRD confirmed the creation of the UiO-66-NH2/Pd NPs. The generated nanocomposite showed impressive catalytic effectiveness in the CC construction by Suzuki-Miyaura reaction (SMC), producing high yields of biaryl products under gentle conditions. The catalyst was very stable and truly heterogeneous, as verified by hot filtration tests. Importantly, the catalyst could be recycled for 7 runs without notable decline in activity, showing its ability as an efficient and stable heterogeneous catalyst for C–C construction process.
这项具有包容性的创新研究成功地将钯纳米颗粒添加到金属有机骨架材料UiO-66-NH2中,并以薰衣草花水提取物为媒介,作为天然还原剂。利用TEM、FE-SEM、EDX、ICP-OES和XRD等方法进行详细分析,证实了UiO-66-NH2/Pd NPs的形成。所制备的纳米复合材料在Suzuki-Miyaura反应(SMC)的CC构建中表现出令人印象深刻的催化效果,在温和的条件下产生高收率的联芳基产物。热过滤实验证实了催化剂的稳定性和多相性。重要的是,该催化剂可以循环使用7次,活性没有明显下降,表明其作为C-C构建过程中高效稳定的多相催化剂的能力。
{"title":"Biosynthesis of a recyclable MOF catalyst (UiO-66-NH2/Pd) mediated by Lavandula angustifolia extract: Investigation of its catalytic activity in Suzuki-Miyaura coupling reactions","authors":"Narinderjit Singh Sawaran Singh ,&nbsp;Rafid Kamal Jameel ,&nbsp;Ahmed Aldulaimi ,&nbsp;Malatesh Akkur ,&nbsp;Satish Kumar Samal ,&nbsp;Sridharan Sundharam ,&nbsp;Sanjeev Kumar ,&nbsp;Khalmurat Iliev ,&nbsp;Zukhra Atamuratova ,&nbsp;D. Yolchiev ,&nbsp;Aseel Smerat ,&nbsp;H. Amin El Sabban","doi":"10.1016/j.jorganchem.2025.123991","DOIUrl":"10.1016/j.jorganchem.2025.123991","url":null,"abstract":"<div><div>This inclusive innovation research achieved the successful addition of palladium nanoparticles into the metal–organic framework material UiO-66-NH<sub>2</sub>, mediated by an aqueous extract of <em>Lavandula angustifolia</em> flower, as a natural reducing agent. Detailed analysis using various methods, such as TEM, FE-SEM, EDX, ICP-OES, and XRD confirmed the creation of the UiO-66-NH<sub>2</sub>/Pd NPs. The generated nanocomposite showed impressive catalytic effectiveness in the C<img>C construction by Suzuki-Miyaura reaction (SMC), producing high yields of biaryl products under gentle conditions. The catalyst was very stable and truly heterogeneous, as verified by hot filtration tests. Importantly, the catalyst could be recycled for 7 runs without notable decline in activity, showing its ability as an efficient and stable heterogeneous catalyst for C–C construction process.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1046 ","pages":"Article 123991"},"PeriodicalIF":2.1,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882121","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}
引用次数: 0
A facile and reusable heterogeneous catalyst for chan- lam coupling reaction 一种易于重复使用的多相催化剂用于chan- lam偶联反应
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-02-01 Epub Date: 2025-12-11 DOI: 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.
Chan-Lam偶联是一种高效的过渡金属催化CN键形成策略,可用于合成各种n-芳基化分子结构。尽管该领域取得了显著的进步,但由于恶劣的反应条件和昂贵的催化剂的使用,构建CN仍然具有挑战性。在此,我们开发了一种易于重复使用的聚合物负载铜催化剂(mPANCu),用于Chan-Lam偶联反应,该催化剂将氯化铜(II)加入到适当的功能化聚丙烯腈(PAN)中。经过详细的表征(FTIR, XRD, XPS, ICPMS和EDAX分析),mPANCu在较温和的反应条件下成功地优化为对苯胺(1a)与苯硼酸(2a)之间的Chan-Lam偶联反应的高效非均相催化剂。在室温条件下,在甲醇中以Na2CO3存在的条件下,用一系列取代苯胺和芳基硼酸进一步确定了该反应的普遍性。此外,该催化剂具有良好的可回收性,通过简单的过滤和重复使用连续的反应循环,而不会在其稳定性和活性上有明显的损失。
{"title":"A facile and reusable heterogeneous catalyst for chan- lam coupling reaction","authors":"Suku Arya ,&nbsp;Fathimathul Rinsana ,&nbsp;Shajahan Rubina ,&nbsp;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":"2026-02-01","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}
引用次数: 0
Well-defined palladium Nheterocyclic carbene complexes bearing CF3 moiety: Synthesis, characterization, crystal structure, direct C4-arylation of 3,5-dimethylisoxazole and antioxidant activity 明确定义的含CF3片段的钯非杂环卡宾配合物:合成、表征、晶体结构、3,5-二甲基异恶唑的直接c4 -芳基化和抗氧化活性
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-02-01 Epub Date: 2025-12-05 DOI: 10.1016/j.jorganchem.2025.123975
Ayşegül Kalçık , Nazan Kaloğlu , Serhat Keser , Zarife Sibel Şahin , Serpil Demir Düşünceli
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.
以{1-(苄基)-3-(3,5-(双(三氟甲基)苄基)苯并咪唑溴}为原料,合成了反式-[Pd(NHC)Br2L] (L = C5H5N, 3- clc5h4n, n -甲基咪唑)和[Pd(NHC)2Br2]等一系列钯n -杂环卡宾(NHC)配合物。这些新化合物的结构通过核磁共振、红外光谱和元素分析得到了证实。用单晶x射线衍射法测定了二溴-[1-(苄基)-3-(3,5-(二(三氟甲基)苄基)苯并咪唑-2-酰基]-(吡啶)钯(II)和二溴-[1-(苄基)-3-(3,5-(二(三氟甲基)苄基)苯并咪唑-2-酰基]-(n -甲基咪唑)钯(II)的晶体结构。钯配合物是3,5-二甲基异恶唑和芳基溴直接c4 -芳基化的高效预催化剂。通过ABTS、OH和DPPH自由基清除活性测定,评价反式[Pd(NHC)Br2L]的生物效率。
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Journal of Organometallic Chemistry
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