Journal of Organometallic Chemistry最新文献

英文中文

A new Schiff-base-N-propylhydrazine-1-carbothioamide complex of copper on boehmite nanoparticles as a recoverable catalyst in the homoselective synthesis of 5-substituted tetrazoles 沸石纳米颗粒上新的席夫碱-N-丙基肼-1-硫代甲酰胺铜络合物作为 5-取代的四唑的同选择性合成中的可回收催化剂

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2024-10-09 DOI: 10.1016/j.jorganchem.2024.123405

Elham Mohseni , Arash Ghorbani-Choghamarani , Bahman Tahmasbi , Masoomeh Norouzi

In this work, 2-(2-hydroxybenzylidene)hydrazine-1-carbothioamide (Schiff-base-HBHCT) was synthesized, and it was identified by FT-IR, ¹H NMR, and ¹³C NMR spectroscopies. Besides, 3-iodopropyltrimethoxysilane (3-IPTMS) was synthesized by a simple S_N2 reaction of 3-chloropropyltrimethoxysilane and potassium iodide in dry acetone. Also, boehmite nanoparticles are synthesized by a simple route and available commercial materials. Then, the surface of boehmite nanoparticles was modified by 3-IPTMS, and then it was further functionalized by Schiff-base-HBHCT. Finally, the copper ion became complex with functionalized Schiff-base-HBHCT (Cu-Schiff-base-HBHCT@boehmite). The particle size and morphology of Cu-Schiff-base-HBHCT@boehmite were studied by SEM images. Organic moieties and elemental composition of Cu-Schiff-base-HBHCT@boehmite were investigated by TGA, AAS, EDS, and WDX analysis. The surface area of Cu-Schiff-base-HBHCT@boehmite was calculated by nitrogen adsorption/desorption analysis, including BJH and BET methods. In the final step, the catalytic application of Cu-Schiff-base-HBHCT@boehmite was studied in the homoselective synthesis of tetrazoles. This catalyst has shown good reusability in the synthesis of tetrazoles.

本研究合成了 2-(2-羟基亚苄基)肼-1-硫代甲酰胺（希夫碱-HBHCT），并通过傅立叶变换红外光谱、1H NMR 和 13C NMR 光谱对其进行了鉴定。此外，3-碘丙基三甲氧基硅烷（3-IPTMS）是由 3-氯丙基三甲氧基硅烷和碘化钾在干丙酮中通过简单的 SN2 反应合成的。此外，还采用简单的方法和现有的商业材料合成了波姆石纳米颗粒。然后，用 3-IPTMS 对纳米勃姆石表面进行修饰，再用 Schiff-base-HBHCT 对其进一步官能化。最后，铜离子与功能化的 Schiff-base-HBHCT 成为络合物（Cu-Schiff-base-HBHCT@boehmite）。通过扫描电镜图像研究了 Cu-Schiff-base-HBHCT@boehmite 的粒度和形态。通过 TGA、AAS、EDS 和 WDX 分析研究了 Cu-Schiff-base-HBHCT@boehmite 的有机分子和元素组成。Cu-Schiff-base-HBHCT@boehmite 的比表面积是通过氮吸附/解吸分析（包括 BJH 和 BET 方法）计算得出的。最后，研究了 Cu-Schiff-base-HBHCT@boehmite 在同选择性合成四氮唑中的催化应用。该催化剂在四唑合成中具有良好的重复使用性。

{"title":"A new Schiff-base-N-propylhydrazine-1-carbothioamide complex of copper on boehmite nanoparticles as a recoverable catalyst in the homoselective synthesis of 5-substituted tetrazoles","authors":"Elham Mohseni , Arash Ghorbani-Choghamarani , Bahman Tahmasbi , Masoomeh Norouzi","doi":"10.1016/j.jorganchem.2024.123405","DOIUrl":"10.1016/j.jorganchem.2024.123405","url":null,"abstract":"<div><div>In this work, 2-(2-hydroxybenzylidene)hydrazine-1-carbothioamide (Schiff-base-HBHCT) was synthesized, and it was identified by FT-IR, 1H NMR, and 13C NMR spectroscopies. Besides, 3-iodopropyltrimethoxysilane (3-IPTMS) was synthesized by a simple SN2 reaction of 3-chloropropyltrimethoxysilane and potassium iodide in dry acetone. Also, boehmite nanoparticles are synthesized by a simple route and available commercial materials. Then, the surface of boehmite nanoparticles was modified by 3-IPTMS, and then it was further functionalized by Schiff-base-HBHCT. Finally, the copper ion became complex with functionalized Schiff-base-HBHCT (Cu-Schiff-base-HBHCT@boehmite). The particle size and morphology of Cu-Schiff-base-HBHCT@boehmite were studied by SEM images. Organic moieties and elemental composition of Cu-Schiff-base-HBHCT@boehmite were investigated by TGA, AAS, EDS, and WDX analysis. The surface area of Cu-Schiff-base-HBHCT@boehmite was calculated by nitrogen adsorption/desorption analysis, including BJH and BET methods. In the final step, the catalytic application of Cu-Schiff-base-HBHCT@boehmite was studied in the homoselective synthesis of tetrazoles. This catalyst has shown good reusability in the synthesis of tetrazoles.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1022 ","pages":"Article 123405"},"PeriodicalIF":2.1,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142433471","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

Recent advances in the chemistry of 2-metallanaphthalenes: 2-telluranaphthalene, 2-stibanaphthalene, 2-stannanaphthalene, 2-germanaphthalene and their analogues 2- 金属萘化学的最新进展：2-碲萘、2-链烷萘、2-链烷萘、2-锗萘及其类似物

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2024-10-09 DOI: 10.1016/j.jorganchem.2024.123407

Hamdy K. Thabet , Mohamed H. Helal , Moustafa A. Gouda

The fusion of benzene with the c edge of 4H-telluropyran, 4H-stanine, 4H-stibinine or 4H-germine 2d motifs in hybrid configurations forms four distinct structures: condensed 2-telluranaphthalene, 2-stibanaphthalene, 2-stannanaphthalene and 2-germanaphthalene (2-metallanaphthalenes). 2-Metallanaphthalene (Metal= Te, Sb, Sn and Ge) is characterized by the presence of a Te, Sb, Sn and Ge atom in the second position instead of the first of 2-metallanaphthalene. To our knowledge, no reports have been published specifically on this scaffold, which has primarily been used as a building block. The synthesis of 2-telluranaphthalene, 2-stibanaphthalene, 2-stannanaphthalene or 2-germanaphthalene and their analogues can be achieved through various chemical pathways, including the Sonogashira coupling reactions, nucleophilic addition, organometallic reactions, metal substitution, and other methods.

苯与 4H-四氢吡喃、4H-链烷、4H-链宾或 4H-锗 2d 基团的 c 边在混合构型中融合形成四种不同的结构：缩合 2-碲萘、2-链烷萘、2-链烷萘和 2-锗萘（2-金属萘）。2-金属萘（金属= Te、Sb、Sn 和 Ge）的特点是在 2-金属萘的第二个位置而不是第一个位置存在 Te、Sb、Sn 和 Ge 原子。据我们所知，目前还没有关于这种支架的专门报道，它主要被用作一种构筑基块。合成 2-碲萘、2-链烷萘、2-锡萘或 2-锗萘及其类似物可通过各种化学途径实现，包括 Sonogashira 偶联反应、亲核加成、有机金属反应、金属取代等方法。

引用次数: 0

Merrifield resin-supported N-heterocyclic carbene-silver complex appended with caffeine for Sonogashira cross-coupling reaction 梅里菲尔德树脂支撑的 N-杂环碳银络合物与咖啡因的索诺伽希拉交叉偶联反应

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2024-10-04 DOI: 10.1016/j.jorganchem.2024.123406

Taha Aalhusaini , Dattaprasad Pore , Gajanan Rashinkar

A novel Merrifield resin-supported N-heterocyclic carbene (NHC)-silver(I) complex, utilizing caffeine as an environmentally friendly NHC precursor, has been synthesized by a multi-step approach. The confirmation of the formation of the complex was achieved through the utilization of a number of analytical methods, including Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), electron dispersive X-ray (EDX), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) analysis. The complex was efficiently used as a highly effective heterogeneous catalyst for the Sonogashira coupling reaction involving aryl halides and terminal alkynes. The complex was retrieved through a straightforward filtration technique, significantly simplifying the purification step and allowed successive reuse for multiple times with minimal loss in activity.

利用咖啡因作为环境友好型 NHC 前体，通过多步骤方法合成了一种新型 Merrifield 树脂支撑的 N-杂环碳烯（NHC）-银（I）络合物。通过使用多种分析方法，包括傅立叶变换红外光谱（FT-IR）、热重分析（TGA）、X 射线光电子能谱（XPS）、X 射线衍射（XRD）、电子分散 X 射线（EDX）、扫描电子显微镜（SEM）和透射电子显微镜（TEM）分析，确认了该复合物的形成。该复合物被有效地用作涉及芳基卤化物和端炔的 Sonogashira 偶联反应的高效异相催化剂。该复合物通过直接过滤技术回收，大大简化了纯化步骤，并可多次重复使用，且活性损失极小。

引用次数: 0

Preparation and characterization of axially substituted silicon phthalocyanine-modified nano TiO2 thin films 轴向取代硅酞菁改性纳米二氧化钛薄膜的制备与表征

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2024-10-04 DOI: 10.1016/j.jorganchem.2024.123408

Hilal Fazlı , Çağla Akkol , Ömer Kesmez , Ece Tugba Saka , Zekeriya Biyiklioglu

Nowadays, reaching of industrial wastes containing durable organic pollutants to water resources is one of the important environmental problems. Cost-effective, nontoxic, thermally and chemically stable, light-sensitive photocatalysts are being developed for the removal of these wastes from water resources. Our aim in this study is to synthesize newly bis-[(4-pyrenebutoxy)]phthalocyaninato silicon (Pyrn-C₄-SiPc) and bis-[n-(9-anthrylmethyl)-n-methylamino]phthalocyaninato silicon (Anthr-C₃-SiPc) molecules and then modify onto TiO₂ nanoparticles. The sol-gel method was used during the modification process to achieve synthesis at lower temperatures to obtain nano TiO₂ crystals in the anatase form. 10% and 25% concentrations of silicon phthalocyanine-modified TiO₂ nanoparticles which are approximately around 5 nm the particle sizes were added to the preparated hybride organic-inorganic polymer network, and were applied to the glass surface by spray method. The resulting coatings’ thicknesses, photocatalytic activities, and optical, physical, morphological, and mechanical properties were tested. The adhesion of the coatings sprayed onto the glass surface was measured as 5B The coatings created were found to have high hardness and resistance in the tests conducted. This research successfully developed photocatalytic hybrid nanocomposite films that are highly transparent with 90% light transmittance exhibit robust photocatalytic activity, and remain color-stable.

如今，含有持久性有机污染物的工业废物进入水资源是重要的环境问题之一。目前正在开发具有成本效益、无毒、热稳定性和化学稳定性的光敏光催化剂，用于清除水资源中的这些废物。本研究旨在合成新的双[(4-芘丁氧基)]酞菁硅（Pyrn-C4-SiPc）和双[n-(9-蒽丙基甲基)-n-甲基氨基]酞菁硅（Anthr-C3-SiPc）分子，然后将其修饰到二氧化钛纳米粒子上。在改性过程中采用了溶胶-凝胶法，以实现在较低温度下合成，从而获得锐钛矿型纳米二氧化钛晶体。在制备好的有机-无机混合聚合物网络中分别加入 10%和 25%浓度的硅酞菁改性 TiO2 纳米粒子（粒径约为 5 纳米），并通过喷涂方法将其涂在玻璃表面。测试了所得涂层的厚度、光催化活性以及光学、物理、形态和机械性能。喷涂到玻璃表面的涂层的附着力测量值为 5B 在进行的测试中发现，所制作的涂层具有很高的硬度和耐受性。这项研究成功开发出了光催化混合纳米复合薄膜，其透光率高达 90%，具有很强的光催化活性，并且颜色稳定。

{"title":"Preparation and characterization of axially substituted silicon phthalocyanine-modified nano TiO2 thin films","authors":"Hilal Fazlı , Çağla Akkol , Ömer Kesmez , Ece Tugba Saka , Zekeriya Biyiklioglu","doi":"10.1016/j.jorganchem.2024.123408","DOIUrl":"10.1016/j.jorganchem.2024.123408","url":null,"abstract":"<div><div>Nowadays, reaching of industrial wastes containing durable organic pollutants to water resources is one of the important environmental problems. Cost-effective, nontoxic, thermally and chemically stable, light-sensitive photocatalysts are being developed for the removal of these wastes from water resources. Our aim in this study is to synthesize newly bis-[(4-pyrenebutoxy)]phthalocyaninato silicon (Pyrn-C4-SiPc) and bis-[n-(9-anthrylmethyl)-n-methylamino]phthalocyaninato silicon (Anthr-C3-SiPc) molecules and then modify onto TiO2 nanoparticles. The sol-gel method was used during the modification process to achieve synthesis at lower temperatures to obtain nano TiO2 crystals in the anatase form. 10% and 25% concentrations of silicon phthalocyanine-modified TiO2 nanoparticles which are approximately around 5 nm the particle sizes were added to the preparated hybride organic-inorganic polymer network, and were applied to the glass surface by spray method. The resulting coatings’ thicknesses, photocatalytic activities, and optical, physical, morphological, and mechanical properties were tested. The adhesion of the coatings sprayed onto the glass surface was measured as 5B The coatings created were found to have high hardness and resistance in the tests conducted. This research successfully developed photocatalytic hybrid nanocomposite films that are highly transparent with 90% light transmittance exhibit robust photocatalytic activity, and remain color-stable.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1022 ","pages":"Article 123408"},"PeriodicalIF":2.1,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142445911","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

Zirconium/niacin metal-organic framework preparation, characterization and assessment as a catalyst in one-pot synthesis of xanthene-1,8-dione derivatives with docking validation as anti-inflammatory 锆/烟酸金属有机框架的制备、表征和评估，作为催化剂用于香蒽-1,8-二酮衍生物的一锅合成以及作为抗炎剂的对接验证

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2024-09-28 DOI: 10.1016/j.jorganchem.2024.123403

Asma S. Al-Wasidi

The zirconium/niacin metal-organic framework (MOF) was prepared by an efficient solvothermal method and the nanostructure of MOF was identified by IR, SEM, EDX, XRD, BET and TEM. The prepared Zr-MOF was evaluated as a catalyst in organic synthesis. Tetrahydro xanthene-1,8‑dione derivatives were synthesized by a one-pot reaction between 2 mol of dimedone and 1 mole of aromatic aldehyde in the presence of the catalytic amount of Zr-MOF under solvent-free conditions. The prepared ligands were evaluated as COX-1 and COX-2 inhibitors and the data obtained explained that the ligands 4-(3,3,6,6-tetramethyl-1,8-dioxo-2,3,4,5,6,7,8,9-octahydro-1H-xanthen-9-yl)phenyl benzoate (3 g), 3,3,6,6-tetramethyl-9-(5-methylfuran-2-yl)-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)‑dione (3i) and 9-(3-(4-chlorophenyl)-1-phenyl-1H-pyrazol-4-yl)-3,3,6,6-tetramethyl-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)‑dione (3j) gave the promised data.

采用高效溶热法制备了锆/烟酸金属有机框架（MOF），并通过红外光谱、扫描电镜、电离辐射X射线、X射线衍射、BET和TEM鉴定了MOF的纳米结构。所制备的 Zr-MOF 在有机合成中作为催化剂进行了评估。在无溶剂条件下，2 摩尔二聚酮和 1 摩尔芳香醛在催化量 Zr-MOF 的存在下发生一锅反应，合成了四氢呫吨-1,8-二酮衍生物。所获得的数据表明，配体 4-(3,3,6,6-四甲基-1,8-二氧代-2,3,4,5,6,7,8,9-八氢-1H-氧杂蒽-9-基)苯基苯甲酸酯（3 克）、3,3,6、6-四甲基-9-(5-甲基呋喃-2-基)-3,4,5,6,7,9-六氢-1H-氧杂蒽-1,8(2H)-二酮 (3i) 和 9-(3-(4-氯苯基)-1-苯基-1H-吡唑-4-基)-3,3,6,6-四甲基-3,4,5,6,7,9-六氢-1H-氧杂蒽-1,8(2H)-二酮 (3j) 得到了答应的数据。

{"title":"Zirconium/niacin metal-organic framework preparation, characterization and assessment as a catalyst in one-pot synthesis of xanthene-1,8-dione derivatives with docking validation as anti-inflammatory","authors":"Asma S. Al-Wasidi","doi":"10.1016/j.jorganchem.2024.123403","DOIUrl":"10.1016/j.jorganchem.2024.123403","url":null,"abstract":"<div><div>The zirconium/niacin metal-organic framework (MOF) was prepared by an efficient solvothermal method and the nanostructure of MOF was identified by IR, SEM, EDX, XRD, BET and TEM. The prepared Zr-MOF was evaluated as a catalyst in organic synthesis. Tetrahydro xanthene-1,8‑dione derivatives were synthesized by a one-pot reaction between 2 mol of dimedone and 1 mole of aromatic aldehyde in the presence of the catalytic amount of Zr-MOF under solvent-free conditions. The prepared ligands were evaluated as COX-1 and COX-2 inhibitors and the data obtained explained that the ligands 4-(3,3,6,6-tetramethyl-1,8-dioxo-2,3,4,5,6,7,8,9-octahydro-1H-xanthen-9-yl)phenyl benzoate (3 g), 3,3,6,6-tetramethyl-9-(5-methylfuran-2-yl)-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)‑dione (3i) and 9-(3-(4-chlorophenyl)-1-phenyl-1H-pyrazol-4-yl)-3,3,6,6-tetramethyl-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)‑dione (3j) gave the promised data.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1022 ","pages":"Article 123403"},"PeriodicalIF":2.1,"publicationDate":"2024-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142425588","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

High-performance ammonium perchlorate propellants enabled by ferrocene-functionalized carbon nanotube catalysts 二茂铁功能化碳纳米管催化剂催化的高性能高氯酸铵推进剂

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2024-09-24 DOI: 10.1016/j.jorganchem.2024.123401

Qun Luo, Xueyi Chang, Zhiyu Cheng, Yongfu Qiu, Guiping Tan, Muqing Chen

Ferrocene-based burning rate catalysts (BRCs) are essential for controlling the combustion of ammonium perchlorate (AP)-based composite solid propellants. However, their efficacy is often limited by migration during storage, leading to performance degradation. This work reports a novel class of covalently grafted ferrocene-functionalized multi-walled carbon nanotubes (CNT-Fc-n, n = 1, 2, 3) exhibiting enhanced catalytic activity and anti-migration properties. Structural characterization confirmed successful functionalization, while electrochemical analysis revealed facilitated electron transfer during AP decomposition due to π-π conjugation within the CNT-Fc-n structure. Consequently, CNT-Fc-n catalysts significantly reduced the AP decomposition activation energy, with CNT-Fc-3 (highest ferrocene loading) demonstrating the most pronounced catalytic effect. Specifically, CNT-Fc-3 lowered the AP decomposition temperature by 103 °C and 39 °C compared to pure AP and Catocene-catalyzed AP, respectively. Kinetic analysis revealed a 28-fold increase in the rate constant for CNT-Fc-3 catalyzed AP decomposition compared to pure AP. Moreover, the unique architecture of CNT-Fc-3 significantly reduced migration during a 50 °C simulation. This work presents a promising strategy for developing high-performance, migration-resistant BRCs for next-generation solid propellants.

二茂铁基燃烧速率催化剂（BRC）对于控制高氯酸铵（AP）基复合固体推进剂的燃烧至关重要。然而，它们的功效往往受到储存过程中迁移的限制，从而导致性能下降。本研究报告了一类新型共价接枝二茂铁功能化多壁碳纳米管（CNT-Fc-n，n = 1、2、3），它们具有更强的催化活性和抗迁移特性。结构表征证实了功能化的成功，而电化学分析表明，CNT-Fc-n 结构中的π-π共轭作用促进了 AP 分解过程中的电子转移。因此，CNT-Fc-n 催化剂显著降低了 AP 分解活化能，其中 CNT-Fc-3（二茂铁负载量最高）的催化作用最为明显。具体而言，与纯 AP 和二茂铁催化的 AP 相比，CNT-Fc-3 将 AP 分解温度分别降低了 103 ℃ 和 39 ℃。动力学分析表明，与纯 AP 相比，CNT-Fc-3 催化 AP 分解的速率常数增加了 28 倍。此外，CNT-Fc-3 的独特结构大大减少了 50 °C 模拟期间的迁移。这项工作为开发用于下一代固体推进剂的高性能、抗迁移 BRC 提供了一种前景广阔的策略。

{"title":"High-performance ammonium perchlorate propellants enabled by ferrocene-functionalized carbon nanotube catalysts","authors":"Qun Luo, Xueyi Chang, Zhiyu Cheng, Yongfu Qiu, Guiping Tan, Muqing Chen","doi":"10.1016/j.jorganchem.2024.123401","DOIUrl":"10.1016/j.jorganchem.2024.123401","url":null,"abstract":"<div><div>Ferrocene-based burning rate catalysts (BRCs) are essential for controlling the combustion of ammonium perchlorate (AP)-based composite solid propellants. However, their efficacy is often limited by migration during storage, leading to performance degradation. This work reports a novel class of covalently grafted ferrocene-functionalized multi-walled carbon nanotubes (CNT-Fc-n, n = 1, 2, 3) exhibiting enhanced catalytic activity and anti-migration properties. Structural characterization confirmed successful functionalization, while electrochemical analysis revealed facilitated electron transfer during AP decomposition due to π-π conjugation within the CNT-Fc-n structure. Consequently, CNT-Fc-n catalysts significantly reduced the AP decomposition activation energy, with CNT-Fc-3 (highest ferrocene loading) demonstrating the most pronounced catalytic effect. Specifically, CNT-Fc-3 lowered the AP decomposition temperature by 103 °C and 39 °C compared to pure AP and Catocene-catalyzed AP, respectively. Kinetic analysis revealed a 28-fold increase in the rate constant for CNT-Fc-3 catalyzed AP decomposition compared to pure AP. Moreover, the unique architecture of CNT-Fc-3 significantly reduced migration during a 50 °C simulation. This work presents a promising strategy for developing high-performance, migration-resistant BRCs for next-generation solid propellants.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1022 ","pages":"Article 123401"},"PeriodicalIF":2.1,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142320228","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

Enhancing quantum capacitance in BNyne/Graphene heterostructures through transition-metal dopants for high-performance supercapacitors 通过过渡金属掺杂剂提高 BNyne/石墨烯异质结构的量子电容，实现高性能超级电容器

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2024-09-24 DOI: 10.1016/j.jorganchem.2024.123404

Miguel Escobar , Maryam Ghareeb , Mustafa Mudhafar , Marwah.J. Hezam , Nouby M. Ghazaly , Shaima Haithem Zaki , Hussam Abdali Abdulridui , Ayodele Lasisi , Saiful Islam

Using Density functional theory (DFT), we investigated the charge storage capacity, quantum capacitance (C_Q), geometry and electronic structures of BNyne/graphene heterostructures (BNyneGHs), as well as the impact of transition-metal dopants on their C_Q. Our results showed that doping was more effective than vacancy defects in improving the C_Q of BNyneGHs. Ti-doped BNyneGHs exhibited the highest C_Q value of 360.08 μF/cm², making them ideal positive electrode materials for supercapacitors (SCs). The presence of doping agents was found to enhance the density of states (DOS) around the Fermi level, resulting in improved C_Q. Our calculations identified potential cathode or anode materials for high-energy-density SCs, providing theoretical support for the design of high-capacitance SCs.

我们利用密度泛函理论（DFT）研究了硼炔/石墨烯异质结构（BNyne/GHs）的电荷存储容量、量子电容（CQ）、几何形状和电子结构，以及过渡金属掺杂物对其 CQ 的影响。我们的研究结果表明，在改善 BNyneGHs 的 CQ 方面，掺杂比空位缺陷更有效。掺杂钛的 BNyneGHs 的 CQ 值最高，达到 360.08 μF/cm2，是超级电容器 (SC) 理想的正极材料。研究发现，掺杂剂的存在提高了费米级附近的状态密度（DOS），从而改善了 CQ。我们的计算为高能量密度超级电容器确定了潜在的阴极或阳极材料，为高电容超级电容器的设计提供了理论支持。

引用次数: 0

A new class of silatranes derived from nitrilotris(methylenephenylphosphinic) acid 从氮三(亚甲基苯基膦酸)衍生出的一类新型硅烷

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2024-09-23 DOI: 10.1016/j.jorganchem.2024.123402

Steven Knerr , Erica Brendler , Jan Zuber , Edwin Kroke , Jörg Wagler

Reactions of a series of trichlorosilanes RSiCl₃ (R = Me, tBu, Bn, Ph, Vi, Cl) and the tris(trimethylsilyl) derivative of nitrilotris(methylenephenylphosphinic) acid (NTPA(SiMe₃)₃) proceeded with transsilylation (release of Me₃SiCl) and afforded the respective silatrane-like cage compounds of the type N(CH₂P(=O)(Ph)O)₃SiR (NTPA(SiR), R = Me, tBu, Bn, Ph, Vi, Cl). According to single-crystal X-ray diffraction analyses (for R = Me, tBu, Bn, Ph, Vi) and DFT analyses (R = Me, Cl), these compounds accommodate [4+1]-coordinate Si atoms in a capped tetrahedral coordination sphere. The environment of the N atom is trigonal pyramidal, with the lone pair pointing toward the Si atom with N⋅⋅⋅Si distances in the range of 2.7451(12) Å (R = Bn) to 2.827(5) Å (R = tBu). For R = Cl, N⋅⋅⋅Si distances were calculated at the PBE0 level to be 2.748 Å in the isolated molecule, 2.620 Å in a chloroform solvate of the type NTPA(SiCl)(HCCl₃)₃. Analyses of the Intrinsic Bond Orbitals (IBOs) and Natural Localized Molecular Orbitals (NLMOs) revealed polarization of the N-located lone pair toward Si, with only marginal orbital contribution of the Si atom in the resultant NLMO (ca. 1.4% for R = hydrocarbyl, 2.2% for R = Cl, 3.3% for R = Cl(HCCl₃)₃).

一系列三氯硅烷 RSiCl3（R = Me、tBu、Bn、Ph、Vi、Cl）和氮基三(亚甲基苯基膦)酸的三(三甲基硅)衍生物（NTPA(SiMe3)3）发生了反式硅烷化反应（释放出 Me3SiCl），并得到了相应的 N(CH2P(=O)(Ph)O)3SiR（NTPA(SiR)，R = Me、tBu、Bn、Ph、Vi、Cl）型硅烷基笼状化合物。根据单晶 X 射线衍射分析（R = Me、tBu、Bn、Ph、Vi）和 DFT 分析（R = Me、Cl），这些化合物的四面体配位层中含有 [4+1] 配位的硅原子。N 原子的环境呈三叉金字塔形，孤对指向硅原子，N⋅⋅⋅Si 间距在 2.7451(12) Å（R = Bn）到 2.827(5) Å（R = tBu）之间。对于 R = Cl，在 PBE0 水平上计算出的 N⋅⋅Si 距离在孤立分子中为 2.748 Å，在 NTPA(SiCl)(HCCl3)3 型氯仿溶液中为 2.620 Å。对固有键轨道 (IBO) 和天然局域分子轨道 (NLMO) 的分析表明，位于 N 位置的孤负对向硅极化，在由此产生的 NLMO 中，硅原子的轨道贡献微不足道（R = 碳氢基时约为 1.4%，R = Cl 时约为 2.2%，R = Cl(HCCl3)3 时约为 3.3%）。

{"title":"A new class of silatranes derived from nitrilotris(methylenephenylphosphinic) acid","authors":"Steven Knerr , Erica Brendler , Jan Zuber , Edwin Kroke , Jörg Wagler","doi":"10.1016/j.jorganchem.2024.123402","DOIUrl":"10.1016/j.jorganchem.2024.123402","url":null,"abstract":"<div><div>Reactions of a series of trichlorosilanes RSiCl3 (R = Me, tBu, Bn, Ph, Vi, Cl) and the tris(trimethylsilyl) derivative of nitrilotris(methylenephenylphosphinic) acid (NTPA(SiMe3)3) proceeded with transsilylation (release of Me3SiCl) and afforded the respective silatrane-like cage compounds of the type N(CH2P(=O)(Ph)O)3SiR (NTPA(SiR), R = Me, tBu, Bn, Ph, Vi, Cl). According to single-crystal X-ray diffraction analyses (for R = Me, tBu, Bn, Ph, Vi) and DFT analyses (R = Me, Cl), these compounds accommodate [4+1]-coordinate Si atoms in a capped tetrahedral coordination sphere. The environment of the N atom is trigonal pyramidal, with the lone pair pointing toward the Si atom with N⋅⋅⋅Si distances in the range of 2.7451(12) Å (R = Bn) to 2.827(5) Å (R = tBu). For R = Cl, N⋅⋅⋅Si distances were calculated at the PBE0 level to be 2.748 Å in the isolated molecule, 2.620 Å in a chloroform solvate of the type NTPA(SiCl)(HCCl3)3. Analyses of the Intrinsic Bond Orbitals (IBOs) and Natural Localized Molecular Orbitals (NLMOs) revealed polarization of the N-located lone pair toward Si, with only marginal orbital contribution of the Si atom in the resultant NLMO (ca. 1.4% for R = hydrocarbyl, 2.2% for R = Cl, 3.3% for R = Cl(HCCl3)3).</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1023 ","pages":"Article 123402"},"PeriodicalIF":2.1,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142593979","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Protective effect of the perchlorophenyl group in organophosphorus chemistry 有机磷化学中高氯苯基的保护作用

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2024-09-23 DOI: 10.1016/j.jorganchem.2024.123385

Mª Ángeles García-Monforte, Miguel Baya, Antonio Martín, Babil Menjón

The homoleptic phosphine with the bulky perchlorophenyl group, (C₆Cl₅)₃P (1), exhibits trigonal pyramidal structure (TPY-3), yet considerably flattened: Σ(C–P–C') = 321.0(1)°. Key steric and electronic properties of this simple organophosphorus species have been estimated by calculation. Attending to its characteristic features, 1 can be rated as a deactivated phosphine, where the less-basic P atom is sterically shielded by the bulky C₆Cl₅ groups. This marked inertness notwithstanding, it has been possible to obtain (under harsh conditions) derivatives with phosphorus in high oxidation state, namely the phosphine oxide (C₆Cl₅)₃PO (2) and the difluorophosphorane (C₆Cl₅)₃PF₂ (3). These four- and five-substituted derivatives respectively exhibit trigonal pyramidal (TPY-4) and trigonal bipyramidal (TBPY-5) structures. The Σ(C–P–C') value steadily increases along the series 1–3, according to the referred structural variation. The P–C bond length is, in turn, invariably maintained at about 185 pm regardless of the different oxidation state, the increasing number of substituents around the P atom and the overall geometry. The hypervalent difluorophosphorane (C₆Cl₅)₃PF₂ (3) dissociates one of the axial fluorides in the gas phase giving rise to the fluorophosphonium cation [(C₆Cl₅)₃PF]⁺, as detected by mass spectrometry. This cation is identified as a Lewis superacid.

带有笨重全氯苯基的同性膦 (C6Cl5)3P (1) 呈三叉金字塔结构 (TPY-3)，但相当扁平：σ(c-p-c') = 321.0(1)°。我们通过计算估算了这种简单有机磷物种的主要立体和电子特性。根据其特征，1 可被定性为一种失活膦，其中碱性较低的 P 原子被体积较大的 C6Cl5 基团立体屏蔽。尽管存在这种明显的惰性，但（在苛刻的条件下）仍有可能获得磷处于高氧化态的衍生物，即氧化膦 (C6Cl5)3PO (2) 和二氟磷烷 (C6Cl5)3PF2 (3)。这些四代和五代衍生物分别呈现出三叉金字塔（TPY-4）和三叉双金字塔（TBPY-5）结构。根据所述的结构变化，Σ(C-P-C')值沿着 1-3 系列稳步上升。反过来，无论氧化态如何变化，P 原子周围取代基的数量和整体几何形状如何增加，P-C 键的长度始终保持在 185 pm 左右。高价二氟磷烷 (C6Cl5)3PF2 (3) 在气相中会解离出一个轴向氟化物，从而产生氟鏻阳离子 [(C6Cl5)3PF]+，质谱法检测到了这一阳离子。这种阳离子被认定为路易斯超酸。

{"title":"Protective effect of the perchlorophenyl group in organophosphorus chemistry","authors":"Mª Ángeles García-Monforte, Miguel Baya, Antonio Martín, Babil Menjón","doi":"10.1016/j.jorganchem.2024.123385","DOIUrl":"10.1016/j.jorganchem.2024.123385","url":null,"abstract":"<div><div>The homoleptic phosphine with the bulky perchlorophenyl group, (C6Cl5)3P (1), exhibits trigonal pyramidal structure (TPY-3), yet considerably flattened: Σ(C–P–C') = 321.0(1)°. Key steric and electronic properties of this simple organophosphorus species have been estimated by calculation. Attending to its characteristic features, 1 can be rated as a deactivated phosphine, where the less-basic P atom is sterically shielded by the bulky C6Cl5 groups. This marked inertness notwithstanding, it has been possible to obtain (under harsh conditions) derivatives with phosphorus in high oxidation state, namely the phosphine oxide (C6Cl5)3PO (2) and the difluorophosphorane (C6Cl5)3PF2 (3). These four- and five-substituted derivatives respectively exhibit trigonal pyramidal (TPY-4) and trigonal bipyramidal (TBPY-5) structures. The Σ(C–P–C') value steadily increases along the series 1–3, according to the referred structural variation. The P–C bond length is, in turn, invariably maintained at about 185 pm regardless of the different oxidation state, the increasing number of substituents around the P atom and the overall geometry. The hypervalent difluorophosphorane (C6Cl5)3PF2 (3) dissociates one of the axial fluorides in the gas phase giving rise to the fluorophosphonium cation [(C6Cl5)3PF]+, as detected by mass spectrometry. This cation is identified as a Lewis superacid.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1022 ","pages":"Article 123385"},"PeriodicalIF":2.1,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142433475","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A sequential olefin hydroboration/Suzuki coupling for denitrogenative alkylation of benzotriazinones with α-olefins 苯并三嗪酮与α-烯烃进行脱氮烷基化的烯烃氢硼化/铃木偶联顺序法

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2024-09-21 DOI: 10.1016/j.jorganchem.2024.123383

Fengze Wang, Yingying Hong, Xuanxuan Zhang, Gang Zou

A denitrogenative alkylation of N-aryl benzotriazinones using readily available α-olefins as alkyl sources via a hydroboration/palladium-catalyzed alkyl Suzuki coupling sequence is reported to afford ortho n-alkyl benzamides in good to excellent yields. Scope and limitations of the sequential hydroboration/Suzuki coupling protocol have been explored, showing large steric effects of both benzotriazinone core and alkylboranes. Only primary alkyl group of trialkylboranes from anti-Markovnikov hydroboration of α-olefins could be effectively coupled, making the protocol highly selective for ortho n-alkyl benzamides.

据报道，使用现成的 α-烯烃作为烷基来源，通过硼氢化/钯催化的烷基铃木偶联顺序，对 N-芳基苯并三嗪酮进行脱氮烷基化反应，可以得到正交 n-烷基苯甲酰胺，收率良好甚至极佳。对氢硼化/铃木偶联顺序的范围和局限性进行了探讨，结果表明苯并三嗪酮核心和烷基硼烷都有很大的立体效应。只有来自 α-olefins 的反马尔科夫尼科夫硼化反应的三烷基硼烷的伯烷基才能有效偶联，这使得该方案对正交正烷基苯甲酰胺具有高度选择性。

引用次数: 0

首页上一页

下一页尾页

类型

全部化学•材料生命科学医学物理工程技术环境•农林材料科学地球科学法学管理学化学环境科学与生态学计算机科学教育学经济学农林科学人文科学生物学数学物理与天体物理心理学综合性期刊其他工业工程理学历史学农学文学信息工程

数据库

全部 ACS Publications Elsevier ieeexplore Springer The Royal Society of Chemistry Wiley

期刊

Journal of Organometallic Chemistry

全部 Acc. Chem. Res. ACS Applied Bio Materials ACS Appl. Electron. Mater. ACS Appl. Energy Mater. ACS Appl. Mater. Interfaces ACS Appl. Nano Mater. ACS Appl. Polym. Mater. ACS BIOMATER-SCI ENG ACS Catal. ACS Cent. Sci. ACS Chem. Biol. ACS Chemical Health & Safety ACS Chem. Neurosci. ACS Comb. Sci. ACS Earth Space Chem. ACS Energy Lett. ACS Infect. Dis. ACS Macro Lett. ACS Mater. Lett. ACS Med. Chem. Lett. ACS Nano ACS Omega ACS Photonics ACS Sens. ACS Sustainable Chem. Eng. ACS Synth. Biol. Anal. Chem. BIOCHEMISTRY-US Bioconjugate Chem. BIOMACROMOLECULES Chem. Res. Toxicol. Chem. Rev. Chem. Mater. CRYST GROWTH DES ENERG FUEL Environ. Sci. Technol. Environ. Sci. Technol. Lett. Eur. J. Inorg. Chem. IND ENG CHEM RES Inorg. Chem. J. Agric. Food. Chem. J. Chem. Eng. Data J. Chem. Educ. J. Chem. Inf. Model. J. Chem. Theory Comput. J. Med. Chem. J. Nat. Prod. J PROTEOME RES J. Am. Chem. Soc. LANGMUIR MACROMOLECULES Mol. Pharmaceutics Nano Lett. Org. Lett. ORG PROCESS RES DEV ORGANOMETALLICS J. Org. Chem. J. Phys. Chem. J. Phys. Chem. A J. Phys. Chem. B J. Phys. Chem. C J. Phys. Chem. Lett. Analyst Anal. Methods Biomater. Sci. Catal. Sci. Technol. Chem. Commun. Chem. Soc. Rev. CHEM EDUC RES PRACT CRYSTENGCOMM Dalton Trans. Energy Environ. Sci. ENVIRON SCI-NANO ENVIRON SCI-PROC IMP ENVIRON SCI-WAT RES Faraday Discuss. Food Funct. Green Chem. Inorg. Chem. Front. Integr. Biol. J. Anal. At. Spectrom. J. Mater. Chem. A J. Mater. Chem. B J. Mater. Chem. C Lab Chip Mater. Chem. Front. Mater. Horiz. MEDCHEMCOMM Metallomics Mol. Biosyst. Mol. Syst. Des. Eng. Nanoscale Nanoscale Horiz. Nat. Prod. Rep. New J. Chem. Org. Biomol. Chem. Org. Chem. Front. PHOTOCH PHOTOBIO SCI PCCP Polym. Chem.

﹀