Journal of Organometallic Chemistry最新文献_第5页

Advancing Suzuki couplings: The role of metal-organic frameworks in efficient biaryl compound synthesis 推进铃木偶联：金属-有机框架在高效联芳基化合物合成中的作用

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-12-04 DOI: 10.1016/j.jorganchem.2025.123961

Khadijeh Rabiei

The reactions that create carbon-carbon bonds have consistently fascinated chemists due to their vast spectrum of applications in organic chemistry. In particular, the Suzuki reaction is renowned for forming C–C bonds, which are utilized to prepare a broad spectrum of biological and pharmaceutical compounds. Furthermore, investigators are endeavoring to develop easy, inexpensive, rapid, and more effective procedures in various coupling reactions, with the Suzuki coupling being a widely employed cross-coupling reaction in current organic synthesis. Metal-organic frameworks (MOFs) have emerged as materials that can serve as solid supports with a large surface area, positioning themselves at the forefront of research in catalysis. Over the past years, MOFs have attracted special attention as a type of organic-inorganic-based material, primarily due to their tunable structures and high porosity, which allow for the incorporation of various metal centers. Notably, they have been utilized for numerous organic transformations as eco-friendly replacements for traditional heterogeneous catalysts, achieving satisfactory catalytic performance while enhancing the efficiency of organic conversion processes. The significance of MOFs is expected to be further underscored in the upcoming 2025 Nobel Prize in Chemistry, as their innovative applications in catalysis could revolutionize the field and offer sustainable solutions to traditional chemical processes. Consequently, MOFs could be an excellent support choice for creating ideal metal-based catalysts, which exhibit greater availability of active sites and remarkable catalytic performance. Ultimately, the primary objective of this review is to highlight the utility of MOF-based catalyst systems in the Suzuki reaction for the construction of valuable biaryl compounds, encompassing developments leading up to 2025.

产生碳-碳键的反应一直吸引着化学家，因为它们在有机化学中的广泛应用。特别是，铃木反应以形成C-C键而闻名，这种键可用于制备广泛的生物和药物化合物。此外，研究人员正在努力开发各种偶联反应的简单，廉价，快速和更有效的程序，铃木偶联是目前有机合成中广泛使用的交叉偶联反应。金属有机框架（mof）作为一种具有大表面积的固体支撑材料，在催化研究中处于前沿地位。在过去的几年里，mof作为一种有机-无机基材料引起了人们的特别关注，主要是因为它们具有可调的结构和高孔隙率，允许加入各种金属中心。值得注意的是，它们已被用于许多有机转化，作为传统多相催化剂的环保替代品，在提高有机转化过程效率的同时取得了令人满意的催化性能。mof的重要性预计将在即将到来的2025年诺贝尔化学奖中得到进一步强调，因为它们在催化方面的创新应用可能会彻底改变这一领域，并为传统化学工艺提供可持续的解决方案。因此，mof是制备理想金属基催化剂的理想载体，具有较高的活性位点可用性和优异的催化性能。最后，本综述的主要目的是强调基于mof的催化剂体系在铃木反应中用于构建有价值的联芳基化合物的应用，包括到2025年的发展。

{"title":"Advancing Suzuki couplings: The role of metal-organic frameworks in efficient biaryl compound synthesis","authors":"Khadijeh Rabiei","doi":"10.1016/j.jorganchem.2025.123961","DOIUrl":"10.1016/j.jorganchem.2025.123961","url":null,"abstract":"<div><div>The reactions that create carbon-carbon bonds have consistently fascinated chemists due to their vast spectrum of applications in organic chemistry. In particular, the Suzuki reaction is renowned for forming C–C bonds, which are utilized to prepare a broad spectrum of biological and pharmaceutical compounds. Furthermore, investigators are endeavoring to develop easy, inexpensive, rapid, and more effective procedures in various coupling reactions, with the Suzuki coupling being a widely employed cross-coupling reaction in current organic synthesis. Metal-organic frameworks (MOFs) have emerged as materials that can serve as solid supports with a large surface area, positioning themselves at the forefront of research in catalysis. Over the past years, MOFs have attracted special attention as a type of organic-inorganic-based material, primarily due to their tunable structures and high porosity, which allow for the incorporation of various metal centers. Notably, they have been utilized for numerous organic transformations as eco-friendly replacements for traditional heterogeneous catalysts, achieving satisfactory catalytic performance while enhancing the efficiency of organic conversion processes. The significance of MOFs is expected to be further underscored in the upcoming 2025 Nobel Prize in Chemistry, as their innovative applications in catalysis could revolutionize the field and offer sustainable solutions to traditional chemical processes. Consequently, MOFs could be an excellent support choice for creating ideal metal-based catalysts, which exhibit greater availability of active sites and remarkable catalytic performance. Ultimately, the primary objective of this review is to highlight the utility of MOF-based catalyst systems in the Suzuki reaction for the construction of valuable biaryl compounds, encompassing developments leading up to 2025.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1045 ","pages":"Article 123961"},"PeriodicalIF":2.1,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748495","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Magnetic carbon nanotubes in multicomponent reactions: A path to sustainable heterocyclic synthesis 多组分反应中的磁性碳纳米管：可持续杂环合成的途径

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-12-03 DOI: 10.1016/j.jorganchem.2025.123971

Mohammad Abushuhel , Radwan Ali , Subbulakshmi Ganesan , Al-Hasnaawei Shaker , Mosstafa Kazemi , Karthikeyan Jayabalan , Renu Sharma , Aashna Sinha

Magnetic carbon nanotubes (MCNTs) have emerged as a versatile class of nanostructured materials that combine the physicochemical properties of carbon nanotubes with the magnetic responsiveness of incorporated nanoparticles. Their high surface area, tunable surface functionality, excellent thermal and chemical stability, and ease of magnetic separation make them particularly attractive as heterogeneous catalysts. In recent years, MCNTs have been extensively explored in multicomponent reactions (MCRs), a powerful synthetic strategy that enables the rapid and atom‐economical construction of structurally diverse heterocycles with pharmaceutical and agrochemical relevance. This review highlights the design, synthesis, and catalytic applications of MCNTs in MCRs leading to nitrogen-, oxygen-, and sulfur-containing heterocycles reported over the past decade. Special emphasis is placed on how surface functionalization and magnetic modification enhance catalytic efficiency, recyclability, and sustainability. Comparative insights into reaction yields, selectivity, and green chemistry metrics are provided, alongside a discussion of mechanistic aspects and structure–activity relationships. This review explores the design, functionalization, and catalytic applications of magnetic carbon nanotubes (MCNTs) in multicomponent synthesis of heterocycles, emphasizing their efficiency, recyclability, and potential for sustainable chemistry. Finally, current challenges and future perspectives are addressed, particularly the integration of MCNTs in scalable and environmentally benign heterocyclic synthesis.

磁性碳纳米管（MCNTs）是一种多用途的纳米结构材料，它结合了碳纳米管的物理化学性质和纳米颗粒的磁性响应性。它们的高表面积，可调节的表面功能，优异的热稳定性和化学稳定性，以及易于磁分离使它们作为异相催化剂特别有吸引力。近年来，mcnt在多组分反应（mcr）中得到了广泛的研究，这是一种强大的合成策略，可以快速和原子经济地构建具有制药和农用化学意义的结构多样的杂环。本文综述了近十年来mcnt的设计、合成和在mcr中的催化应用，这些应用导致了含氮、含氧和含硫的杂环。特别强调的是表面功能化和磁改性如何提高催化效率，可回收性和可持续性。提供了对反应产率，选择性和绿色化学指标的比较见解，以及对机理方面和构效关系的讨论。本文综述了磁性碳纳米管（MCNTs）的设计、功能化及其在多组分杂环合成中的催化应用，强调了其效率、可回收性和可持续化学潜力。最后，讨论了当前的挑战和未来的前景，特别是mcnt在可扩展和环境友好的杂环合成中的集成。

{"title":"Magnetic carbon nanotubes in multicomponent reactions: A path to sustainable heterocyclic synthesis","authors":"Mohammad Abushuhel , Radwan Ali , Subbulakshmi Ganesan , Al-Hasnaawei Shaker , Mosstafa Kazemi , Karthikeyan Jayabalan , Renu Sharma , Aashna Sinha","doi":"10.1016/j.jorganchem.2025.123971","DOIUrl":"10.1016/j.jorganchem.2025.123971","url":null,"abstract":"<div><div>Magnetic carbon nanotubes (MCNTs) have emerged as a versatile class of nanostructured materials that combine the physicochemical properties of carbon nanotubes with the magnetic responsiveness of incorporated nanoparticles. Their high surface area, tunable surface functionality, excellent thermal and chemical stability, and ease of magnetic separation make them particularly attractive as heterogeneous catalysts. In recent years, MCNTs have been extensively explored in multicomponent reactions (MCRs), a powerful synthetic strategy that enables the rapid and atom‐economical construction of structurally diverse heterocycles with pharmaceutical and agrochemical relevance. This review highlights the design, synthesis, and catalytic applications of MCNTs in MCRs leading to nitrogen-, oxygen-, and sulfur-containing heterocycles reported over the past decade. Special emphasis is placed on how surface functionalization and magnetic modification enhance catalytic efficiency, recyclability, and sustainability. Comparative insights into reaction yields, selectivity, and green chemistry metrics are provided, alongside a discussion of mechanistic aspects and structure–activity relationships. This review explores the design, functionalization, and catalytic applications of magnetic carbon nanotubes (MCNTs) in multicomponent synthesis of heterocycles, emphasizing their efficiency, recyclability, and potential for sustainable chemistry. Finally, current challenges and future perspectives are addressed, particularly the integration of MCNTs in scalable and environmentally benign heterocyclic synthesis.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1045 ","pages":"Article 123971"},"PeriodicalIF":2.1,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748497","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Silver nanoparticles immobilized over Zn–Al-layered double hydroxide as a heterogeneous catalyst for synthesis of chromene derivatives 银纳米颗粒在锌-铝层双氢氧化物上作为合成铬衍生物的非均相催化剂

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-12-03 DOI: 10.1016/j.jorganchem.2025.123970

Ali B.M. Ali , Ammar Yasir Ahmed , Narinderjit Singh Sawaran Singh , Alejandro Pérez-Larios , Carlos Soto-Robles , Osmin Áviles-García , P. Jangir , Mustafa Diab , H. Amin El Sabban , Mutabar Latipova , Ruslanbek Siddikov , Mumtaj Shah

This exclusive innovation work presents the creation and development of silver nanoparticles coated Mentha pulegium extract-enhanced Zn–Al-layered double hydroxide (Zn-Al LDH/MPextract), a novel nanocatalyst. The created Zn-Al LDH/MPextract served as an effective protective and reducing framework for the in situ formation of Ag NPs. A wide array of cutting-edge techniques, such as TEM, FE-SEM, EDX, ICP-OES, elemental mapping, and XRD, were utilized to investigate the structural properties of the Zn-Al LDH/MPextract/Ag nanoparticles. The catalytic efficiency of the Zn-Al LDH/MPextract/Ag NPs was examined for the generation of 2-amino-4H-chromenes through a 3-component condensation involving resorcinol, aldehydes, and malononitrile. The Zn-Al LDH/MPextract/Ag NPs nanocatalyst was shown good recyclability until 6 cycles without notable decrease in its performance.

这项独家创新工作展示了一种新型纳米催化剂——镀银纳米颗粒薄荷提取物增强锌铝层状双氢氧化物（Zn-Al LDH/MPextract）的创造和开发。制备的Zn-Al LDH/ mp提取物对Ag NPs的原位形成起到了有效的保护和还原框架作用。利用TEM、FE-SEM、EDX、ICP-OES、元素映射和XRD等尖端技术研究了Zn-Al LDH/MPextract/Ag纳米颗粒的结构特性。考察了Zn-Al LDH/ mp提取物/Ag NPs通过间苯二酚、醛和丙二腈三组分缩合反应生成2-氨基-4 - h -铬的催化效率。Zn-Al LDH/MPextract/Ag NPs纳米催化剂具有良好的可回收性，循环6次后其性能没有明显下降。

{"title":"Silver nanoparticles immobilized over Zn–Al-layered double hydroxide as a heterogeneous catalyst for synthesis of chromene derivatives","authors":"Ali B.M. Ali , Ammar Yasir Ahmed , Narinderjit Singh Sawaran Singh , Alejandro Pérez-Larios , Carlos Soto-Robles , Osmin Áviles-García , P. Jangir , Mustafa Diab , H. Amin El Sabban , Mutabar Latipova , Ruslanbek Siddikov , Mumtaj Shah","doi":"10.1016/j.jorganchem.2025.123970","DOIUrl":"10.1016/j.jorganchem.2025.123970","url":null,"abstract":"<div><div>This exclusive innovation work presents the creation and development of silver nanoparticles coated <em>Mentha pulegium</em> extract-enhanced Zn–Al-layered double hydroxide (Zn-Al LDH/MPextract), a novel nanocatalyst. The created Zn-Al LDH/MPextract served as an effective protective and reducing framework for the in <em>situ</em> formation of Ag NPs. A wide array of cutting-edge techniques, such as TEM, FE-SEM, EDX, ICP-OES, elemental mapping, and XRD, were utilized to investigate the structural properties of the Zn-Al LDH/MPextract/Ag nanoparticles. The catalytic efficiency of the Zn-Al LDH/MPextract/Ag NPs was examined for the generation of 2-amino-4H-chromenes through a 3-component condensation involving resorcinol, aldehydes, and malononitrile. The Zn-Al LDH/MPextract/Ag NPs nanocatalyst was shown good recyclability until 6 cycles without notable decrease in its performance.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1045 ","pages":"Article 123970"},"PeriodicalIF":2.1,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748496","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

Towards understanding the molecular mechanism of Cadiot-Chodkiewicz cross-coupling reaction Cadiot-Chodkiewicz交叉偶联反应分子机理的探讨

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-12-03 DOI: 10.1016/j.jorganchem.2025.123969

C Rajalakshmi , Lakshmi Anil , Harry Wilson , Leemol Roy , Gopinathan Anilkumar , Vibin Ipe Thomas

The Cadiot-Chodkiewicz cross-coupling reaction is an important synthetic method in which terminal alkynes couple with alkynyl halides in the presence of transition metal catalysts to produce unsymmetrical 1,3-diynes. Among the different transition metal catalysts, zinc has recently garnered significant attention due to its affordability and environmentally benign characteristics. Computational studies on the catalytic mechanisms of Cadiot-Chodkiewicz cross-coupling reactions remain scarce, despite significant progress in their experimental methodologies. In this study, we present a detailed mechanistic investigation of the Zn-catalyzed Cadiot Chodkiewicz cross-coupling reaction between p-tolyl acetylene and 1-bromo phenyl acetylene using the Density Functional Theory (DFT) method. The catalytic pathway commences with base-assisted transmetalation, subsequently proceeding through a concerted nucleophilic substitution-reductive elimination sequence. The mechanism adheres to a redox-neutral pathway, wherein the catalytic zinc center remains in the +2 oxidation state throughout the catalytic cycle. This in-depth analysis of the reaction pathway provides crucial insights for designing more sustainable protocols for the synthesis of unsymmetrical 1,3-diynes.

Cadiot-Chodkiewicz交叉偶联反应是在过渡金属催化剂存在下，末端炔与炔卤偶联生成不对称1,3-二炔的一种重要合成方法。在不同的过渡金属催化剂中，锌由于其可负担性和环境友好的特性最近引起了人们的极大关注。Cadiot-Chodkiewicz交叉偶联反应的催化机理的计算研究仍然很少，尽管他们的实验方法取得了重大进展。本文采用密度泛函理论（DFT）方法对zn催化的对甲苯乙炔与1-溴苯基乙炔Cadiot Chodkiewicz交叉偶联反应进行了详细的机理研究。催化途径从碱基辅助金属转化开始，随后经过一致的亲核取代-还原消除序列。该机制遵循氧化还原-中性途径，其中催化锌中心在整个催化循环中保持+2氧化态。这种对反应途径的深入分析为设计更可持续的合成不对称1,3-二炔的方案提供了重要的见解。

{"title":"Towards understanding the molecular mechanism of Cadiot-Chodkiewicz cross-coupling reaction","authors":"C Rajalakshmi , Lakshmi Anil , Harry Wilson , Leemol Roy , Gopinathan Anilkumar , Vibin Ipe Thomas","doi":"10.1016/j.jorganchem.2025.123969","DOIUrl":"10.1016/j.jorganchem.2025.123969","url":null,"abstract":"<div><div>The Cadiot-Chodkiewicz cross-coupling reaction is an important synthetic method in which terminal alkynes couple with alkynyl halides in the presence of transition metal catalysts to produce unsymmetrical 1,3-diynes. Among the different transition metal catalysts, zinc has recently garnered significant attention due to its affordability and environmentally benign characteristics. Computational studies on the catalytic mechanisms of Cadiot-Chodkiewicz cross-coupling reactions remain scarce, despite significant progress in their experimental methodologies. In this study, we present a detailed mechanistic investigation of the Zn-catalyzed Cadiot Chodkiewicz cross-coupling reaction between <em>p</em>-tolyl acetylene and 1-bromo phenyl acetylene using the Density Functional Theory (DFT) method. The catalytic pathway commences with base-assisted transmetalation, subsequently proceeding through a concerted nucleophilic substitution-reductive elimination sequence. The mechanism adheres to a redox-neutral pathway, wherein the catalytic zinc center remains in the +2 oxidation state throughout the catalytic cycle. This in-depth analysis of the reaction pathway provides crucial insights for designing more sustainable protocols for the synthesis of unsymmetrical 1,3-diynes.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1045 ","pages":"Article 123969"},"PeriodicalIF":2.1,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748576","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

Fabrication and characterization of APTMS-TCT-GO-Piperazine-Pd nanoparticle as a heterogeneous and reusable catalyst for Suzuki-Miyaura cross-coupling reaction under thermal and microwave conditions 热微波条件下aptms - tct - go -哌嗪- pd纳米颗粒的制备与表征

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-11-26 DOI: 10.1016/j.jorganchem.2025.123960

Athmar Ali Kadhim , Muhammad Abdel Hasan Shallal , Karrar Majeed Obaid , Hayfaa A. Mubarak

This study highlights the critical role of novel Pd-based nanocatalysts in advancing sustainable organic synthesis, particularly in cross-coupling reactions. In this study, a hybrid catalyst was fabricated by functionalizing graphene oxide (GO) with 3-aminopropyltrimethoxysilane (APTMS), 2,4,6-trichloro-1,3,5-triazine (TCT), and piperazine, followed by immobilization of palladium nanoparticles (APTMS-TCT-GO-Piperazine-Pd Nanoparticle). The synthesis of APTMS-TCT-GO-Piperazine-Pd involved multiple steps, including GO preparation via Hummer’s method, surface functionalization with APTMS, further modification with TCT, linkage with piperazine, and finally, Pd nanoparticle loading. Comprehensive characterization techniques such as Field Emission Scanning Electron Microscopy (FE-SEM), Fourier Transform Infrared spectroscopy (FT-IR), X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), and Thermogravimetric Analysis (TGA) confirmed successful fabrication, with Pd nanoparticles averaging 12.5 nm in size and high Pd loading (∼226 ppm). The catalyst demonstrated exceptional efficiency in Suzuki–Miyaura cross-coupling reactions under both thermal and microwave conditions. Optimum conditions included using K₂CO₃ as base in a water/DMF solvent system, yielding biaryl products in high yields (82–97 %) across various aryl halides, including challenging chlorides. Reaction times ranged from minutes under microwave irradiation to hours thermally, with excellent catalyst recyclability over at least seven consecutive cycles, retaining high activity and minimal Pd leaching. The catalyst's advantageous features easy separation, reusability, broad substrate scope, operational simplicity, and outstanding yield highlight its potential for sustainable industrial applications, notably in pharmaceutical and materials synthesis, aligning with eco-friendly and economic objectives in catalysis research.

这项研究强调了新型钯基纳米催化剂在促进可持续有机合成，特别是在交叉偶联反应中的关键作用。在这项研究中，通过3-氨基丙基三甲氧基硅烷（APTMS）、2,4,6-三氯-1,3,5-三嗪（TCT）和哌嗪功能化氧化石墨烯（GO），然后固定化钯纳米颗粒（APTMS-TCT-GO-哌嗪- pd纳米颗粒），制备了一种杂化催化剂。APTMS-TCT-GO-哌嗪-Pd的合成涉及多个步骤，包括通过Hummer的方法制备氧化石墨烯，用APTMS进行表面功能化，用TCT进一步修饰，与哌嗪连接，最后装载钯纳米颗粒。综合表征技术，如场发射扫描电镜（FE-SEM）、傅里叶变换红外光谱（FT-IR）、x射线衍射（XRD）、x射线光电子能谱（XPS）和热重分析（TGA）证实了Pd纳米颗粒的成功制备，平均尺寸为12.5 nm， Pd负载高（~ 226 ppm）。该催化剂在热和微波条件下均表现出优异的Suzuki-Miyaura交叉偶联反应效率。最佳条件包括在水/DMF溶剂体系中使用K₂CO₃作为碱，在各种芳基卤化物中以高收率（82 - 97%）生产联芳基产品，包括具有挑战性的氯化物。反应时间从微波照射下的几分钟到热照射下的几小时不等，催化剂具有优异的可回收性，至少连续七个循环，保持高活性和最小的Pd浸出。该催化剂具有易于分离、可重复使用、广泛的底物范围、操作简单和出色的产量等优点，突出了其可持续工业应用的潜力，特别是在制药和材料合成方面，符合催化研究的生态友好和经济目标。

{"title":"Fabrication and characterization of APTMS-TCT-GO-Piperazine-Pd nanoparticle as a heterogeneous and reusable catalyst for Suzuki-Miyaura cross-coupling reaction under thermal and microwave conditions","authors":"Athmar Ali Kadhim , Muhammad Abdel Hasan Shallal , Karrar Majeed Obaid , Hayfaa A. Mubarak","doi":"10.1016/j.jorganchem.2025.123960","DOIUrl":"10.1016/j.jorganchem.2025.123960","url":null,"abstract":"<div><div>This study highlights the critical role of novel Pd-based nanocatalysts in advancing sustainable organic synthesis, particularly in cross-coupling reactions. In this study, a hybrid catalyst was fabricated by functionalizing graphene oxide (GO) with 3-aminopropyltrimethoxysilane (APTMS), 2,4,6-trichloro-1,3,5-triazine (TCT), and piperazine, followed by immobilization of palladium nanoparticles (APTMS-TCT-GO-Piperazine-Pd Nanoparticle). The synthesis of APTMS-TCT-GO-Piperazine-Pd involved multiple steps, including GO preparation via Hummer’s method, surface functionalization with APTMS, further modification with TCT, linkage with piperazine, and finally, Pd nanoparticle loading. Comprehensive characterization techniques such as Field Emission Scanning Electron Microscopy (FE-SEM), Fourier Transform Infrared spectroscopy (FT-IR), X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), and Thermogravimetric Analysis (TGA) confirmed successful fabrication, with Pd nanoparticles averaging 12.5 nm in size and high Pd loading (∼226 ppm). The catalyst demonstrated exceptional efficiency in Suzuki–Miyaura cross-coupling reactions under both thermal and microwave conditions. Optimum conditions included using K₂CO₃ as base in a water/DMF solvent system, yielding biaryl products in high yields (82–97 %) across various aryl halides, including challenging chlorides. Reaction times ranged from minutes under microwave irradiation to hours thermally, with excellent catalyst recyclability over at least seven consecutive cycles, retaining high activity and minimal Pd leaching. The catalyst's advantageous features easy separation, reusability, broad substrate scope, operational simplicity, and outstanding yield highlight its potential for sustainable industrial applications, notably in pharmaceutical and materials synthesis, aligning with eco-friendly and economic objectives in catalysis research.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1045 ","pages":"Article 123960"},"PeriodicalIF":2.1,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145645624","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

Chemistry and bioactivity of ferrocenyl quinone methides 二茂铁基醌类化合物的化学性质及生物活性

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-11-24 DOI: 10.1016/j.jorganchem.2025.123958

Michael J. McGlinchey

The antiproliferative behaviour of the ferrocifens, derived by replacing a phenyl substituent in tamoxifen by ferrocenyl, and also in their diphenol counterparts, against both ER+ and ER- breast cancers may be attributed to two key factors: the redox-mediated formation of reactive oxygen species (ROS), and the formation of ferrocenyl quinone methides (Fc-QMs) that react with nucleophilic thiols, and also inhibit the ability of thioredoxin reductase to function, thereby weakening the cell’s defence towards ROS. Metabolites arising from the reactions of these Fc-QMs are generated from a variety of novel reactions and molecular rearrangements. These include the formation of dihydrofurans and pyrans, spirobonded tetrahydrofurans, and ferrocenyl migrations, all arising in a stepwise manner via the intermediacy of ferrocenyl-stabilized quinone methide cations. X-ray crystal structures of Fc-QMs bearing alkyl-imido substituents reveal the existence of novel lone pair-π* interactions that enhance their stabilities and lifetimes and allow a rationalisation of their effectiveness against a wide range of tumours.

通过用二茂铁取代他莫昔芬中的苯基取代基，以及其双酚类替代物衍生出的二茂铁对ER+和ER-乳腺癌的抗增殖行为可能归因于两个关键因素：氧化还原介导的活性氧（ROS）的形成，以及与亲核硫醇反应的二茂铁基醌（Fc-QMs）的形成，也会抑制硫氧还蛋白还原酶的功能，从而削弱细胞对ROS的防御能力。这些Fc-QMs反应产生的代谢物是由各种新的反应和分子重排产生的。这些包括二氢呋喃和吡喃的形成，螺键四氢呋喃和二茂铁基迁移，所有这些都是通过二茂铁基稳定的醌类甲基阳离子的中间作用逐步产生的。含有烷基酰亚胺取代基的Fc-QMs的x射线晶体结构揭示了新的孤对π*相互作用的存在，这种相互作用增强了它们的稳定性和寿命，并使它们对各种肿瘤的有效性合理化。

引用次数: 0

Green generation of silver nanoparticles mediated by Mentha pulegium leaf extract: Investigation of its catalytic activity in the A3 coupling reaction, and its anti-cervical cancer effects 薄荷叶提取物介导的绿色代纳米银：A3偶联反应的催化活性及抗宫颈癌作用的研究

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-11-24 DOI: 10.1016/j.jorganchem.2025.123959

Jin Zhang , Zhan Zhou

The application of nanobiotechnology in the detection and treatment of contemporary illnesses has expanded quickly. At low concentrations, biosynthesized silver nanoparticles (AgNPs) offer biomedical qualities and are an environmentally friendly, economical, and biocompatible method. In this study, we used the leaves of Mentha pulegium to report on biogenic supported silver nanoparticles. The leaves of Mentha pulegium were utilized as a green reducing agent and a superior stabilizer for the silver nanoparticles that were synthesized. The created Ag NPs/M. pulegium has been characterized using UV–Vis, TEM, FE-SEM, EDX, and ICP-OES. Further, the catalytic performance of this navel material has been examined in the generation of pyrimido[1,2-b]indazole compounds via A³ coupling reaction between aldehydes, ethynylbenzene and 3-aminoindazoles with good yields under solid-state conditions. Once the reaction was finished, the Ag NPs/M. pulegium catalyst could be easily recycled and used again for 5 runs without remarkable decrease in its efficiency. Ag NPs that were biologically produced were evaluated for their anti-human cervical cancer properties against cell line of cervical cancer. By using the MTT assay, Ag NPs' anti-cervical cancer qualities could effectively eradicate the HeLa cancer cells that was dependent on both concentration and time. Ag NPs induce cell death, which is followed by downregulation of the anti-apoptotic marker Bcl-2 and overexpression of the pro-apoptotic markers Bax and cleaved caspase-8. Furthermore, in contrast to their corresponding control, Ag NPs prevented colony formation. More significantly, the investigation of treated cells molecular pathway with Ag NPs showed that Ag NPs inhibited the expression of PI3K-Akt-mTOR signaling pathway in cells. This implies that the nanoparticles pharmacological effects on human cervical cancer cells were mostly caused by PI3K-Akt-mTOR signaling pathway.

纳米生物技术在当代疾病的检测和治疗中的应用迅速扩大。在低浓度下，生物合成银纳米粒子（AgNPs）具有生物医学特性，是一种环境友好、经济、生物相容性好的方法。在本研究中，我们利用薄荷叶报道了生物负载银纳米粒子。利用薄荷叶作为绿色还原剂和稳定剂制备银纳米粒子。创建的Ag np /M。采用UV-Vis、TEM、FE-SEM、EDX、ICP-OES等对其进行了表征。此外，还考察了该材料在固体条件下通过醛、乙基苯和3-氨基茚唑的A3偶联反应生成嘧啶[1,2-b]茚唑化合物的催化性能，并取得了良好的产率。一旦反应结束，Ag NPs/M。Pulegium催化剂可以很容易地回收利用，重复使用5次，效率没有明显下降。生物制备的Ag NPs对宫颈癌细胞系的抗人宫颈癌特性进行了评价。通过MTT检测，Ag NPs的抗宫颈癌特性可以有效地根除HeLa癌细胞，这种特性与浓度和时间都有依赖性。Ag NPs诱导细胞死亡，随后是抗凋亡标记物Bcl-2下调，促凋亡标记物Bax和cleaved caspase-8过表达。此外，与相应的对照相比，Ag NPs阻止了菌落的形成。更重要的是，Ag NPs对处理细胞分子通路的研究表明，Ag NPs抑制细胞中PI3K-Akt-mTOR信号通路的表达。这表明纳米颗粒对人宫颈癌细胞的药理作用主要是由PI3K-Akt-mTOR信号通路引起的。

{"title":"Green generation of silver nanoparticles mediated by Mentha pulegium leaf extract: Investigation of its catalytic activity in the A3 coupling reaction, and its anti-cervical cancer effects","authors":"Jin Zhang , Zhan Zhou","doi":"10.1016/j.jorganchem.2025.123959","DOIUrl":"10.1016/j.jorganchem.2025.123959","url":null,"abstract":"<div><div>The application of nanobiotechnology in the detection and treatment of contemporary illnesses has expanded quickly. At low concentrations, biosynthesized silver nanoparticles (AgNPs) offer biomedical qualities and are an environmentally friendly, economical, and biocompatible method. In this study, we used the leaves of <em>Mentha pulegium</em> to report on biogenic supported silver nanoparticles. The leaves of <em>Mentha pulegium</em> were utilized as a green reducing agent and a superior stabilizer for the silver nanoparticles that were synthesized. The created Ag NPs/<em>M. pulegium</em> has been characterized using UV–Vis, TEM, FE-SEM, EDX, and ICP-OES. Further, the catalytic performance of this navel material has been examined in the generation of pyrimido[1,2-b]indazole compounds via A<sup>3</sup> coupling reaction between aldehydes, ethynylbenzene and 3-aminoindazoles with good yields under solid-state conditions. Once the reaction was finished, the Ag NPs/<em>M. pulegium</em> catalyst could be easily recycled and used again for 5 runs without remarkable decrease in its efficiency. Ag NPs that were biologically produced were evaluated for their anti-human cervical cancer properties against cell line of cervical cancer. By using the MTT assay, Ag NPs' anti-cervical cancer qualities could effectively eradicate the HeLa cancer cells that was dependent on both concentration and time. Ag NPs induce cell death, which is followed by downregulation of the anti-apoptotic marker Bcl-2 and overexpression of the pro-apoptotic markers Bax and cleaved caspase-8. Furthermore, in contrast to their corresponding control, Ag NPs prevented colony formation. More significantly, the investigation of treated cells molecular pathway with Ag NPs showed that Ag NPs inhibited the expression of PI3K-Akt-mTOR signaling pathway in cells. This implies that the nanoparticles pharmacological effects on human cervical cancer cells were mostly caused by PI3K-Akt-mTOR signaling pathway.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1045 ","pages":"Article 123959"},"PeriodicalIF":2.1,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145692552","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

Green synthesis of silver nanoparticles as an efficient catalyst for one-pot preparation of pyrano[2,3-d]pyrimidines 绿色合成纳米银作为一锅法制备吡喃[2,3-d]嘧啶的高效催化剂

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-11-21 DOI: 10.1016/j.jorganchem.2025.123957

Ali M Hussein , Narinderjit Singh Sawaran Singh , Luma Hussain Saleh , Malatesh Akkur , Satish Kumar Samal , Sridharan Sundharam , Sanjeev Kumar , Khalmurat Iliev , Zukhra Atamuratova , Davronbek Yulchiev , Aseel Smerat , H. El Sabban

In this inclusive innovation research, we have successfully synthesized mono-dispersed silver nanoparticles mediated by Pistacia leaves extract as reducing and stabilizing agent. The reduction in Ag⁺ ions to Ag⁰ nanoparticles was visually proved by a change in color from green to gray color. The present study employs numerous analytical methods like UV–Vis, FT-IR, TEM, SEM, EDX, ICP-OES, elemental mapping, XRD to identify the characteristics of the Ag NPs/Pistacia nanocomposite. TEM analysis revealed the spherical shapes of nanoparticles that have sizes of around 20–30 nm. Due to Importance of pyrano[2,3-d]pyrimidines in pharmaceutical science and their pharmacological activities, we interested to apply Ag NPs/Pistacia as efficient catalyst in the production of pyrano[2,3-d]pyrimidines via a three-component condensation that included barbituric acid, aryl aldehydes, and malononitrile. Furthermore, the Ag NPs/Pistacia catalyst demonstrated commendable recyclability, sustaining its catalytic efficacy after being utilized 7 times with minimal reduction in performance. Easy separation of products, purification without need to column chromatographic, and use of commercially available low-cost substrates make the protocol viable in organic synthesis.

在这项包容性创新研究中，我们成功合成了以黄连木叶提取物为还原剂和稳定剂的单分散纳米银。Ag+离子还原成Ag0纳米粒子，颜色从绿色变为灰色，从视觉上证明了这一点。本研究采用UV-Vis、FT-IR、TEM、SEM、EDX、ICP-OES、元素图谱、XRD等多种分析方法对银纳米颗粒/黄连木纳米复合材料进行了表征。透射电镜分析显示，纳米颗粒的大小约为20-30纳米。鉴于吡喃[2,3-d]嘧啶在制药科学中的重要性及其药理活性，我们有意将Ag NPs/Pistacia作为高效催化剂，通过包括巴比妥酸、芳醛和丙二腈的三组分缩合反应生产吡喃[2,3-d]嘧啶。此外，Ag NPs/Pistacia催化剂表现出值得称赞的可回收性，在使用7次后仍保持其催化效果，性能下降最小。产品易于分离，无需柱层析纯化，以及使用市售的低成本底物，使该方案在有机合成中可行。

{"title":"Green synthesis of silver nanoparticles as an efficient catalyst for one-pot preparation of pyrano[2,3-d]pyrimidines","authors":"Ali M Hussein , Narinderjit Singh Sawaran Singh , Luma Hussain Saleh , Malatesh Akkur , Satish Kumar Samal , Sridharan Sundharam , Sanjeev Kumar , Khalmurat Iliev , Zukhra Atamuratova , Davronbek Yulchiev , Aseel Smerat , H. El Sabban","doi":"10.1016/j.jorganchem.2025.123957","DOIUrl":"10.1016/j.jorganchem.2025.123957","url":null,"abstract":"<div><div>In this inclusive innovation research, we have successfully synthesized mono-dispersed silver nanoparticles mediated by <em>Pistacia</em> leaves extract as reducing and stabilizing agent. The reduction in Ag<sup>+</sup> ions to Ag<sup>0</sup> nanoparticles was visually proved by a change in color from green to gray color. The present study employs numerous analytical methods like UV–Vis, FT-IR, TEM, SEM, EDX, ICP-OES, elemental mapping, XRD to identify the characteristics of the Ag NPs/<em>Pistacia</em> nanocomposite. TEM analysis revealed the spherical shapes of nanoparticles that have sizes of around 20–30 nm. Due to Importance of pyrano[2,3-d]pyrimidines in pharmaceutical science and their pharmacological activities, we interested to apply Ag NPs/<em>Pistacia</em> as efficient catalyst in the production of pyrano[2,3-d]pyrimidines via a three-component condensation that included barbituric acid, aryl aldehydes, and malononitrile. Furthermore, the Ag NPs/<em>Pistacia</em> catalyst demonstrated commendable recyclability, sustaining its catalytic efficacy after being utilized 7 times with minimal reduction in performance. Easy separation of products, purification without need to column chromatographic, and use of commercially available low-cost substrates make the protocol viable in organic synthesis.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1044 ","pages":"Article 123957"},"PeriodicalIF":2.1,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145615607","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

Synthesis, characterization, and photovoltaic performance of two new platina-ynes functionalized with seven-ring fused dithienoindacenodithiophene spacers 两种新型七环熔接二硫代吲哚代二硫代噻吩隔层功能化铂炔的合成、表征及光伏性能

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-11-20 DOI: 10.1016/j.jorganchem.2025.123943

Rayya A. Al Balushi , Najat Al Riyami , Ashanul Haque , Khalaf M. Alenezi , Muhammad S. Khan , Jonathan M. Skelton

This work reports the synthesis, thermal characterization and optical characterization of a novel Pt(II) di‑yne (M) and poly‑yne (P) incorporating a seven-ring fused (2,8-disubstituted-6,12-dihydro-6,6,12,12-tetrakis(4-octylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene) spacer. The nature of the electronic excitation and the effect of conjugation were studied using time-dependent density-functional theory (TD-DFT) calculations. The model complex (M) and the poly‑yne (P) were used as donor materials to fabricate bulk heterojunction polymer solar cells (PSCs) by blending with a [6,6]-phenyl C₇₁-butyric acid methyl ester (PC₇₁BM) as an electron acceptor. The materials show high thermal stability and absorption in the visible region of the spectrum. Computational modelling shows that alkynylation of the fused dithienoindacenodithiophene spacer, and its subsequent incorporation into a Pt(II) di‑yne, results in a reduction of the HOMO-LUMO gap and concomitant red shift of the absorption edge, and a significant enhancement in the oscillator strength. Both M and P were found to show low photovoltaic performance, tentatively attributed to a limited absorption profile. Overall, this study sheds light on a new member of the family of Pt(II) di-ynes and poly-ynes, for which the electronic properties of the materials can be tuned via linker groups with extended aromatic character.

本文报道了一种含有七环熔融（2,8-二取代-6,12-二氢-6,6,12,12-四基（4-辛基苯基）-二噻吩[2,3-d:2 ',3 ' -d]-s-吲哚基[1,2-b:5,6-b ']二噻吩）的新型Pt（II）二炔(M)和聚炔(P)的合成、热表征和光学表征。利用时变密度泛函理论（TD-DFT）计算研究了电子激发的性质和共轭效应。以模型配合物(M)和聚炔(P)为供体材料，以[6,6]-苯基c71 -丁酸甲酯（PC71BM）为电子受体共混制备了体异质结聚合物太阳能电池（PSCs）。材料在光谱可见区表现出较高的热稳定性和吸收率。计算模型表明，融合二噻吩二噻吩的炔基化及其随后加入到Pt（II）二炔中，导致HOMO-LUMO间隙减小和吸收边的伴随红移，并显着增强了振荡器强度。发现M和P均表现出较低的光伏性能，初步归因于有限的吸收剖面。总的来说，本研究揭示了Pt（II）双炔和多炔家族的新成员，其材料的电子性质可以通过具有扩展芳香特征的连接基团来调节。

{"title":"Synthesis, characterization, and photovoltaic performance of two new platina-ynes functionalized with seven-ring fused dithienoindacenodithiophene spacers","authors":"Rayya A. Al Balushi , Najat Al Riyami , Ashanul Haque , Khalaf M. Alenezi , Muhammad S. Khan , Jonathan M. Skelton","doi":"10.1016/j.jorganchem.2025.123943","DOIUrl":"10.1016/j.jorganchem.2025.123943","url":null,"abstract":"<div><div>This work reports the synthesis, thermal characterization and optical characterization of a novel Pt(II) di‑yne (<strong>M</strong>) and poly‑yne (<strong>P</strong>) incorporating a seven-ring fused (2,8-disubstituted-6,12-dihydro-6,6,12,12-tetrakis(4-octylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene) spacer. The nature of the electronic excitation and the effect of conjugation were studied using time-dependent density-functional theory (TD-DFT) calculations. The model complex (<strong>M</strong>) and the poly‑yne (<strong>P</strong>) were used as donor materials to fabricate bulk heterojunction polymer solar cells (PSCs) by blending with a [6,6]-phenyl C<sub>71</sub>-butyric acid methyl ester (PC<sub>71</sub>BM) as an electron acceptor. The materials show high thermal stability and absorption in the visible region of the spectrum. Computational modelling shows that alkynylation of the fused dithienoindacenodithiophene spacer, and its subsequent incorporation into a Pt(II) di‑yne, results in a reduction of the HOMO-LUMO gap and concomitant red shift of the absorption edge, and a significant enhancement in the oscillator strength. Both <strong>M</strong> and <strong>P</strong> were found to show low photovoltaic performance, tentatively attributed to a limited absorption profile. Overall, this study sheds light on a new member of the family of Pt(II) di-ynes and poly-ynes, for which the electronic properties of the materials can be tuned <em>via</em> linker groups with extended aromatic character.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1045 ","pages":"Article 123943"},"PeriodicalIF":2.1,"publicationDate":"2025-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145692611","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

Arylhydrazone–thiazolyne derived Pd–CNN pincer complexes for carbonylative Suzuki coupling, via iron pentacarbonyl as a sustainable CO surrogate 芳酰腙-噻唑啉衍生的Pd-CNN钳形配合物羰基铃木偶联，通过五羰基铁作为可持续的CO替代物

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-11-20 DOI: 10.1016/j.jorganchem.2025.123954

Alberto Reyes-Deloso , Juan Guillermo Robledo-Ayala , Emir A. Galván-García , Rodolfo Goméz-Balderas , José Guillermo Penieres-Carrillo , Fernando Ortega-Jiménez

We report the efficient synthesis and characterization of novel non-symmetric Pd-CNN pincer complexes via C–H bond activation on arylhydrazone-thioether ligands, which serve as effective catalytic precursors for carbonylative Suzuki coupling reactions. The complexes were synthesized using arylhydrazone-thiazolyne ligands, exhibiting enhanced stability and reactivity under ambient conditions. Their catalytic performance was evaluated using Fe(CO)₅ as a carbon monoxide surrogate, addressing the limitations of traditional methods that often involve toxic CO_(g) sources. Actually, Fe(CO)₅ is considered a more practical CO source compared to gaseous CO due to its safer handling and ability to release CO in a controlled manner under reaction conditions; additionally, it is commercially available, cost-effective, and generates minimal metal waste, offering a more sustainable alternative for carbonylative transformations in synthetic chemistry. The optimized reaction conditions yielded significant product formation, with various aryl and heteroaryl halides successfully coupled to produce biaryl ketones, including an antineoplastic agent. The findings highlight the versatility and efficiency of the synthesized pincer complexes in carbonylative Suzuki coupling, paving the way for safer and more effective synthetic methodologies in organic chemistry. A computational study of the Suzuki carbonylative coupling catalytic cycle, using Fe(CO)₅ as the CO source, revealed low energy barriers for key steps and a favorable overall energy profile (ΔE = –33.96 kcal/mol), supporting the experimental efficiency observed. The evaluation of two alternative mechanistic pathways showed that the initial CO coordination plays a decisive thermodynamic role in determining the preferred route through the catalytic cycle, balancing kinetic accessibility and overall stability. These results are consistent with the suitability of Fe(CO)₅ as an effective CO surrogate in carbonylative cross-coupling reactions.

本文报道了在芳酰腙-硫醚配体上通过C-H键激活高效合成和表征新型非对称Pd-CNN螯合物，该螯合物可作为羰基化铃木偶联反应的有效催化前体。用芳酰腙-噻唑啉配体合成的配合物在环境条件下表现出更高的稳定性和反应活性。使用Fe(CO)5作为一氧化碳替代物来评估它们的催化性能，解决了传统方法通常涉及有毒CO(g)源的局限性。实际上，与气态CO相比，Fe（CO）₅被认为是更实用的CO源，因为它更安全的处理和在反应条件下以受控方式释放CO的能力；此外，它是商业上可用的，具有成本效益，并且产生的金属废物最少，为合成化学中的羰基化转化提供了更可持续的替代方案。优化后的反应条件产生了显著的产物，各种芳基和杂芳基卤化物成功偶联生成了联芳基酮，包括一种抗肿瘤药。研究结果突出了羰基化Suzuki偶联钳形配合物的多功能性和效率，为有机化学中更安全、更有效的合成方法铺平了道路。以Fe(CO)5为CO源的Suzuki羰基化偶联催化循环的计算研究表明，关键步骤的能量势垒较低，总体能量分布较好（ΔE = -33.96 kcal/mol），支持实验观察到的效率。对两种可选机理的评价表明，初始CO配位在确定催化循环的优选途径、平衡动力学可及性和总体稳定性方面起决定性的热力学作用。这些结果与Fe(CO)5作为羰基化交叉偶联反应中有效的CO替代物的适用性相一致。

{"title":"Arylhydrazone–thiazolyne derived Pd–CNN pincer complexes for carbonylative Suzuki coupling, via iron pentacarbonyl as a sustainable CO surrogate","authors":"Alberto Reyes-Deloso , Juan Guillermo Robledo-Ayala , Emir A. Galván-García , Rodolfo Goméz-Balderas , José Guillermo Penieres-Carrillo , Fernando Ortega-Jiménez","doi":"10.1016/j.jorganchem.2025.123954","DOIUrl":"10.1016/j.jorganchem.2025.123954","url":null,"abstract":"<div><div>We report the efficient synthesis and characterization of novel non-symmetric Pd-CNN pincer complexes via C–H bond activation on arylhydrazone-thioether ligands, which serve as effective catalytic precursors for carbonylative Suzuki coupling reactions. The complexes were synthesized using arylhydrazone-thiazolyne ligands, exhibiting enhanced stability and reactivity under ambient conditions. Their catalytic performance was evaluated using Fe(CO)<sub>5</sub> as a carbon monoxide surrogate, addressing the limitations of traditional methods that often involve toxic CO<sub>(g)</sub> sources. Actually, Fe(CO)₅ is considered a more practical CO source compared to gaseous CO due to its safer handling and ability to release CO in a controlled manner under reaction conditions; additionally, it is commercially available, cost-effective, and generates minimal metal waste, offering a more sustainable alternative for carbonylative transformations in synthetic chemistry. The optimized reaction conditions yielded significant product formation, with various aryl and heteroaryl halides successfully coupled to produce biaryl ketones, including an antineoplastic agent. The findings highlight the versatility and efficiency of the synthesized pincer complexes in carbonylative Suzuki coupling, paving the way for safer and more effective synthetic methodologies in organic chemistry. A computational study of the Suzuki carbonylative coupling catalytic cycle, using Fe(CO)<sub>5</sub> as the CO source, revealed low energy barriers for key steps and a favorable overall energy profile (ΔE = –33.96 kcal/mol), supporting the experimental efficiency observed. The evaluation of two alternative mechanistic pathways showed that the initial CO coordination plays a decisive thermodynamic role in determining the preferred route through the catalytic cycle, balancing kinetic accessibility and overall stability. These results are consistent with the suitability of Fe(CO)<sub>5</sub> as an effective CO surrogate in carbonylative cross-coupling reactions.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1044 ","pages":"Article 123954"},"PeriodicalIF":2.1,"publicationDate":"2025-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145615609","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