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Synthesis and evaluation of palladium-functionalized biochar-supported magnetic nanoparticles for efficient nitro reduction 用于高效硝基还原的钯功能化生物炭支撑磁性纳米粒子的合成与评估
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-08-22 DOI: 10.1016/j.jorganchem.2024.123314
Fatemeh Gholamrezaei, S. Yousef Ebrahimipour, Ehsan Ghonchepour

This study investigated the catalytic activity of the magnetic Fe3O4@Bio-R-Pd (Bio = biochar, R = epichlorohydrin and guanidine) for the reduction of nitro compounds. The structural and magnetic properties of the synthesized nanocatalyst were characterized using a suite of techniques including inductively coupled plasma spectrometry (ICP), vibrating sample magnetometer (VSM), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), Fourier Transform infrared (FT-IR) spectroscopy, and X-ray diffraction (XRD). The recyclability of the synthesized nanocatalyst was confirmed by its complete reversibility upon testing with a vibrating magnetometer, further supporting its paramagnetic nature. Analysis of the SEM images revealed the presence of spherical magnetite particles within the composite. Using these optimized conditions, various aromatic nitro compounds were successfully reduced in the presence of the Fe3O4@Bio-R-Pd catalyst. The results demonstrate the advantageous properties of the synthesized nanocatalyst, including high product yield, stability and resistance at high temperatures, easy separation from the reaction medium, high efficiency with short reaction times, and economic viability. Notably, the synthesized sample exhibited nearly the same initial efficiency after 5 reuses, indicating almost complete recovery and minimal change in its catalytic activity.

本研究调查了磁性 Fe3O4@Bio-R-Pd(Bio = 生物炭,R = 环氧氯丙烷和胍)还原硝基化合物的催化活性。利用电感耦合等离子体光谱仪 (ICP)、振动样品磁力计 (VSM)、热重分析 (TGA)、扫描电子显微镜 (SEM)、能量色散 X 射线分析 (EDAX)、傅立叶变换红外光谱仪 (FT-IR) 和 X 射线衍射 (XRD) 等一系列技术对合成的纳米催化剂的结构和磁性能进行了表征。合成的纳米催化剂在用振动磁力计测试时完全可逆,这证实了它的可回收性,进一步证明了它的顺磁性。扫描电镜图像分析表明,复合材料中存在球形磁铁矿颗粒。利用这些优化条件,各种芳香族硝基化合物在 Fe3O4@Bio-R-Pd 催化剂存在下被成功还原。研究结果表明,合成的纳米催化剂具有高产率、高温下的稳定性和耐受性、易于从反应介质中分离、反应时间短效率高以及经济可行性等优点。值得注意的是,合成的样品在重复使用 5 次后,效率几乎与初始效率相同,表明其催化活性几乎完全恢复且变化极小。
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引用次数: 0
Revisiting the early days of conjugated polyyne synthesis. Syntheses and structures of Bis(triethylsilyl) Polyynediyl Adducts Et3Si(CC)nSiEt3 previously regarded as Unisolable (n = 6, 8, 12) 重温共轭聚炔合成的早期历程。双(三乙基硅)聚炔二基加合物 Et3Si(CC)nSiEt3(n = 6、8、12)的合成和结构,以前曾被认为是不可分离的
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-08-22 DOI: 10.1016/j.jorganchem.2024.123308
Sourajit Dey Baksi, Aayushi Arora, Nattamai Bhuvanesh, Joseph H. Reibenspies, John A. Gladysz

An overview of bis(trialkylsilyl) polyynediyl adducts R3Si(CC)nSiR3 with n ≥ 5 is followed by syntheses of TESCxTES where x = 8, 12, 16, and 24 (TES = SiEt3; x = 2n). In a seminal 1972 study, the last three were presented as too unstable to isolate and thus only characterized by UV-visible spectroscopy. Although not a rational route, TESC24TES is consistently obtained from the reaction of trans-(C6F5)(p-tol3P)2Pt(CC)5SiEt3 and crude HC8TES under Hay oxidative cross coupling conditions. The latter contains some HC8H and TESC8TES. Hay oxidative homocouplings of HC4TES and crude HC8TES afford TESC8TES (83%) and TESC16TES (5%). A Cadiot-Chodkiewicz reaction of BrC4Br and HC4TES (2 equiv) yields TESC12TES (11%). All of these compounds are crystalline, and the crystal structures of TESC8TES and TESC16TES are determined. The 13C{1H} NMR and UV-visible properties are also compared.

在概述了 n ≥ 5 的双(三烷基硅基)聚炔二基加合物 R3Si(CC)nSiR3 之后,我们合成了 TESCxTES,其中 x = 8、12、16 和 24(TES = SiEt3;x = 2n)。在 1972 年的一项开创性研究中,后三种物质由于太不稳定而无法分离,因此只能通过紫外-可见光谱进行表征。TESC24TES 虽然不是一条合理的路线,但在干草氧化交叉偶联条件下,反式-(C6F5)(p-tol3P)2Pt(CC)5SiEt3 和粗 HC8TES 的反应始终可以得到 TESC24TES。后者含有一些 HC8H 和 TESC8TES。HC4TES 和粗 HC8TES 的 Hay 氧化同偶联反应可生成 TESC8TES(83%)和 TESC16TES(5%)。BrC4Br 和 HC4TES(2 等量)的 Cadiot-Chodkiewicz 反应可生成 TESC12TES(11%)。所有这些化合物都是晶体,并确定了 TESC8TES 和 TESC16TES 的晶体结构。13C{1H}NMR 和紫外可见光特性进行了比较。
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引用次数: 0
rGO/CuO NC catalyzed green synthesis, DFT studies, Mulliken atomic charge analysis and anti-inflammatory activity of indole derivatives rGO/CuO NC 催化吲哚衍生物的绿色合成、DFT 研究、Mulliken 原子电荷分析和抗炎活性
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-08-20 DOI: 10.1016/j.jorganchem.2024.123322
Ravina Meena , Abhinav Raj Khandelwal , Khushboo Sharma , Narsingh Khatik , Harlal Singh , Sarita Khaturia , Harshita Sachdeva

An admirable catalytic activity of as-prepared copper oxide decorated reduced graphene oxide nanocomposite (rGO/CuO NC) catalyst is reported in the synthesis of spiro[indoline-pyranothiazole]carbonitrile and thiazolopyranofuroindole derivatives. The excellent activity exhibited by hybrid nanocomposite is attributed to the synergistic effect of graphene oxide and copper oxide nanoparticles. The utilization of ultrasonication as energy source lead to enhanced mass transfer, and reaction rate expeditiousness in the presence of rGO/CuO NC forming spiro/condensed indole derivatives. 100% conversion is observed on Thin Layer Chromatography (TLC). The recovered rGO/CuO NC can be reused for four uninterrupted cycles without substantial loss in its catalytic activity. DFT (Density functional theory) studies, Mulliken atomic charge analysis and anti-inflammatory activity of the synthesized spiro/condensed indole derivatives have also been evaluated.

据报道,在合成螺[吲哚啉-吡喃噻唑]腈和噻唑并吡喃呋喃吲哚衍生物的过程中,制备的氧化铜装饰还原氧化石墨烯纳米复合材料(rGO/CuO NC)催化剂具有令人赞叹的催化活性。混合纳米复合材料表现出的优异活性归功于氧化石墨烯和氧化铜纳米颗粒的协同效应。在 rGO/CuO NC 的存在下,利用超声波作为能量源可增强传质,加快反应速度,从而形成螺/缩合吲哚衍生物。在薄层色谱法(TLC)上可观察到 100% 的转化率。回收的 rGO/CuO NC 可以不间断地重复使用四次,其催化活性不会有实质性的损失。此外,还对合成的螺/缩吲哚衍生物的 DFT(密度泛函理论)研究、Mulliken 原子电荷分析和抗炎活性进行了评估。
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引用次数: 0
A scorpion-like NHC Ag(I) complex based on triazinetrione: Preparation, structure and recognition to dihydrogen phosphate 基于三嗪三酮的蝎子状 NHC Ag(I) 复合物:制备、结构和对磷酸二氢的识别
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-08-20 DOI: 10.1016/j.jorganchem.2024.123328
Zhi-Xiang Zhao, Yue Yang, Xing-Jun Han, Rui Liu, Qing-Xiang Liu

A tri-imidazolium salt LH3·(PF6)3 and its NHC (N-heterocyclic carbene) Ag(I) complex 1 were prepared and characterized. The structures of LH3·(PF6)3 and 1 were demonstrated by X-ray diffraction analysis. In LH3·(PF6)3, two imidazoles lied on the same side of triazinetrione plane, and the third imidazole lied on another side of triazinetrione plane. Complex 1 was of a scorpion-like structure with a 12-membered macrometallocycle. Additionally, the selective recognition of 1 for H2PO4- was studied on the basis of fluorescent spectra, 1H NMR, MS and IR. The high association constant for 1·H2PO4- (K = 3.3 × 104 M-1) showed that 1 had strong association ability to H2PO4-. The low detection limit (2.54 × 10-10 mol/L) indicated that the detection of 1 to H2PO4- was sensitive.

制备并表征了一种三咪唑盐 LH3-(PF6)3 及其 NHC(N-杂环碳烯)Ag(I) 复合物 1。X 射线衍射分析证明了 LH3-(PF6)3 和 1 的结构。在 LH3-(PF6)3 中,两个咪唑位于三嗪三酮平面的同一侧,第三个咪唑位于三嗪三酮平面的另一侧。络合物 1 具有 12 元大金属环的蝎子状结构。此外,还根据荧光光谱、1H NMR、质谱和红外光谱研究了 1 对 H2PO4- 的选择性识别。1-H2PO4- 的高结合常数(K = 3.3 × 104 M-1)表明 1 与 H2PO4- 的结合能力很强。低检测限(2.54 × 10-10 mol/L)表明 1 对 H2PO4- 的检测是灵敏的。
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引用次数: 0
An eco-friendly convenient approach for the synthesis of guar gum integrated copper nanoparticles: Investigation of its catalytic activity in the CN Ullmann coupling reactions and study of its anti-human kidney cancer effects 一种环保便捷的瓜尔胶集成铜纳米粒子的合成方法:其在 CN 乌尔曼偶联反应中的催化活性及其抗人类肾癌作用的研究
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-08-20 DOI: 10.1016/j.jorganchem.2024.123329
Nana Li , Xiu Wang , Shanshan Kong

We carried out this research was in order to evaluate the potency of guar gum (GG) hydrogel to conduct CuO NPs synthesis by adopting an eco-friendly approach as well as to study its role as catalyst and in relieving cancerous cell lines. In this context, we accomplished the CuO NPs/GG synthesis by employing a simple one-step approach and identified its characters through UV–Visible (UV–Vis) spectroscopy, X-ray diffraction (XRD), transmission electronic microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-rays spectroscopy (EDS), elemental mapping and ICP-OES analysis. XRD and TEM results of CuO NPs/GG showed the face centered cubic (fcc) structures and predominantly spherical shaped with a size of 20–30 nm. After the characterization, the prepared CuO NPs/GG nanocatalyst was used as catalyst in the N-arylation of amines (indole and imidazoles) through C(aryl)-N chemical bond arrangement from the related aryl halides (I, Br, Cl) by Ullmann-type coupling reactions. It is worth mentioning that the novel catalyst has the potential of being recycled seven times without much change in activity. Furthermore, the anti-kidney cancer properties of CuO NPs/GG nanocomposite were assessed by MTT assay about the cytotoxicity and anti-human on normal (HUVEC) and human kidney cell lines i.e. ACHN, CaKi-2 and HEC293. The corresponding IC50 values were 18.5, 17.2, and 15.6 µg/mL, respectively. The viability of malignant human kidney cell line reduced dose-dependently in the presence of the nano bio-composite. After clinical study, CuO NPs/GG nano bio-composite can be utilized as an efficient drug in the treatment of human kidney cancer in human.

我们进行这项研究的目的是评估瓜尔胶(GG)水凝胶采用环保方法合成 CuO NPs 的有效性,并研究其作为催化剂和缓解癌细胞系的作用。在此背景下,我们采用简单的一步法合成了 CuO NPs/GG,并通过紫外可见光谱(UV-Vis)、X 射线衍射(XRD)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、能量色散 X 射线光谱(EDS)、元素图谱和 ICP-OES 分析确定了其特性。CuO NPs/GG 的 XRD 和 TEM 结果显示其为面心立方(ccc)结构,主要呈球形,大小为 20-30 纳米。经表征后,制备的 CuO NPs/GG 纳米催化剂被用作催化剂,通过乌尔曼型偶联反应,以相关芳基卤化物(I、Br、Cl)为原料,通过 C(芳基)-N 化学键排列对胺(吲哚和咪唑)进行 N-芳基化反应。值得一提的是,这种新型催化剂可以循环使用七次,而活性不会有太大变化。此外,CuO NPs/GG 纳米复合材料的抗肾癌特性是通过 MTT 法评估其对正常(HUVEC)和人类肾细胞系(即 ACHN、CaKi-2 和 HEC293)的细胞毒性和抗人类性。相应的 IC50 值分别为 18.5、17.2 和 15.6 µg/mL。在纳米生物复合材料的作用下,恶性人类肾脏细胞系的存活率呈剂量依赖性降低。经过临床研究,CuO NPs/GG 纳米生物复合材料可作为治疗人类肾癌的有效药物。
{"title":"An eco-friendly convenient approach for the synthesis of guar gum integrated copper nanoparticles: Investigation of its catalytic activity in the CN Ullmann coupling reactions and study of its anti-human kidney cancer effects","authors":"Nana Li ,&nbsp;Xiu Wang ,&nbsp;Shanshan Kong","doi":"10.1016/j.jorganchem.2024.123329","DOIUrl":"10.1016/j.jorganchem.2024.123329","url":null,"abstract":"<div><p>We carried out this research was in order to evaluate the potency of guar gum (GG) hydrogel to conduct CuO NPs synthesis by adopting an eco-friendly approach as well as to study its role as catalyst and in relieving cancerous cell lines. In this context, we accomplished the CuO NPs/GG synthesis by employing a simple one-step approach and identified its characters through UV–Visible (UV–Vis) spectroscopy, X-ray diffraction (XRD), transmission electronic microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-rays spectroscopy (EDS), elemental mapping and ICP-OES analysis. XRD and TEM results of CuO NPs/GG showed the face centered cubic (<em>fcc</em>) structures and predominantly spherical shaped with a size of 20–30 nm. After the characterization, the prepared CuO NPs/GG nanocatalyst was used as catalyst in the <em>N</em>-arylation of amines (indole and imidazoles) through C(aryl)-N chemical bond arrangement from the related aryl halides (I, Br, Cl) by Ullmann-type coupling reactions. It is worth mentioning that the novel catalyst has the potential of being recycled seven times without much change in activity. Furthermore, the anti-kidney cancer properties of CuO NPs/GG nanocomposite were assessed by MTT assay about the cytotoxicity and anti-human on normal (HUVEC) and human kidney cell lines i.e. ACHN, CaKi-2 and HEC293. The corresponding IC<sub>50</sub> values were 18.5, 17.2, and 15.6 µg/mL, respectively. The viability of malignant human kidney cell line reduced dose-dependently in the presence of the nano bio-composite. After clinical study, CuO NPs/GG nano bio-composite can be utilized as an efficient drug in the treatment of human kidney cancer in human.</p></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1020 ","pages":"Article 123329"},"PeriodicalIF":2.1,"publicationDate":"2024-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142077521","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, structure, characterization and one pot catalytic activity of half-sandwich iridium(III) complexes 半三明治铱(III)配合物的合成、结构、表征和一锅催化活性
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-08-20 DOI: 10.1016/j.jorganchem.2024.123331
Neelakandan Devika , Subbiah Ananthalakshmi , Nandhagopal Raja , Gajendra Gupta , Bruno Therrien

A series of stable mononuclear half-sandwich iridium(III) complexes of the general formula [(η5-C5Me5)Ir(L)Cl](BPh4) has been synthesized in dry methanol using different imino pyridine ligands (L1–L6) and [(η5-C5Me5)2Ir2(µ-Cl)2Cl2] in a 2:1 molar ratio. All complexes were fully characterized by melting point, CHN analysis, FT-IR, UV–visible, 1H NMR, 13C NMR spectroscopy and mass spectrometry. The structure of complex 3 [(η5-C5Me5)Ir(L3)Cl](BPh4) was determined by single crystal X-ray structure analysis, showing a chelating coordination mode of the imino pyridine L3. One pot organic transformations of aldehyde to amide were carried out by complexes 1–6 in toluene at 110 °C in the presence of hydroxyl amine hydrochloride and sodium bicarbonate. The catalytic activity of complex 3 was found to be excellent, showing high conversion with catalytic turnover frequency up to 500.

利用不同的亚氨基吡啶配体(L1-L6)和[(η5-C5Me5)2Ir2(µ-Cl)2Cl2]以 2:1 的摩尔比在干燥甲醇中合成了一系列通式为[(η5-C5Me5)Ir(L)Cl](BPh4)的稳定单核半夹心铱(III)配合物。所有复合物均通过熔点、碳氢化合物分析、傅立叶变换红外光谱、紫外可见光光谱、1H NMR 光谱、13C NMR 光谱和质谱分析进行了全面表征。通过单晶 X 射线结构分析确定了复合物 3 [(η5-C5Me5)Ir(L3)Cl](BPh4)的结构,显示了亚氨基吡啶 L3 的螯合配位模式。络合物 1-6 在羟胺盐酸盐和碳酸氢钠存在下,于 110 ℃ 在甲苯中实现了醛到酰胺的一锅有机转化。研究发现,络合物 3 的催化活性极佳,转化率高,催化翻转频率高达 500 次。
{"title":"Synthesis, structure, characterization and one pot catalytic activity of half-sandwich iridium(III) complexes","authors":"Neelakandan Devika ,&nbsp;Subbiah Ananthalakshmi ,&nbsp;Nandhagopal Raja ,&nbsp;Gajendra Gupta ,&nbsp;Bruno Therrien","doi":"10.1016/j.jorganchem.2024.123331","DOIUrl":"10.1016/j.jorganchem.2024.123331","url":null,"abstract":"<div><p>A series of stable mononuclear half-sandwich iridium(III) complexes of the general formula [(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Ir(L)Cl](BPh<sub>4</sub>) has been synthesized in dry methanol using different imino pyridine ligands (L<sub>1</sub>–L<sub>6</sub>) and [(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>Ir<sub>2</sub>(µ-Cl)<sub>2</sub>Cl<sub>2</sub>] in a 2:1 molar ratio. All complexes were fully characterized by melting point, CHN analysis, FT-IR, UV–visible, <sup>1</sup>H NMR, <sup>13</sup>C NMR spectroscopy and mass spectrometry. The structure of complex <strong>3</strong> [(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Ir(L<sub>3</sub>)Cl](BPh<sub>4</sub>) was determined by single crystal X-ray structure analysis, showing a chelating coordination mode of the imino pyridine L<sub>3</sub>. One pot organic transformations of aldehyde to amide were carried out by complexes <strong>1–6</strong> in toluene at 110 °C in the presence of hydroxyl amine hydrochloride and sodium bicarbonate. The catalytic activity of complex <strong>3</strong> was found to be excellent, showing high conversion with catalytic turnover frequency up to 500.</p></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1020 ","pages":"Article 123331"},"PeriodicalIF":2.1,"publicationDate":"2024-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142084203","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
Spectroscopic and computational characterization of lanthanide-mediated bond activation of ethylamine 镧系元素介导的乙胺键活化的光谱学和计算表征
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-08-19 DOI: 10.1016/j.jorganchem.2024.123330
Silver Nyambo, Yuchen Zhang, Dong-Sheng Yang

Ln (Ln = La and Ce) atom reactions with ethylamine are conducted in a pulsed laser vaporization supersonic molecular beam source. Dehydrogenation and association metal-containing species are observed with time-of-flight mass spectrometry, and the dehydrogenated Ln ethylimido species in the formula Ln(NC2H5) are characterized by single-photon mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical calculations. The theoretical calculations include density functional theory for both Ln species and a scalar relativity correction, electron correlation, and spin-orbit coupling through multiconfiguration quasi-degenerate second-order perturbation theory for the Ce species. The MATI spectrum of lanthanum ethylimido La(NCH2CH3) has a single vibronic band system from the ionization of the doublet ground state with the La 6s1 configuration, whereas that of the cerium ethylimido Ce(NCH2CH3) displays two vibronic band system from the ionization of the two lowest-energy spin-orbit coupling states with the Ce 4f16s1 configuration. Both Ln ethylimido complexes are formed by the thermodynamically and kinetically favorable concerted dehydrogenation of the amino group. Two additional isomers of Ln(NC2H5) include a four-membered metallacycle Ln(NHCH2CH2) from the dehydrogenation of the amino and methyl groups and a three-membered cycle Ln(NHCHCH3) from the dehydrogenation of the amino and methylene groups. The cyclic isomers are not observed experimentally as they are not populated under the experimental conditions.

在脉冲激光气化超音速分子束源中进行了 Ln(Ln = La 和 Ce)原子与乙胺的反应。利用飞行时间质谱法观察了脱氢和关联的含金属物种,并通过单光子质量分析阈值电离(MATI)光谱和量子化学计算对脱氢的 Ln 乙亚胺物种进行了表征。理论计算包括 Ln 物种的密度泛函理论,以及 Ce 物种的标量相对论校正、电子相关和通过多配置准退化二阶扰动理论进行的自旋轨道耦合。乙基亚氨基镧 La(NCH2CH3) 的 MATI 谱具有一个单振子带系统,它是由 La 6s1 构型的双基态电离产生的;而乙基亚氨基铈 Ce(NCH2CH3) 的 MATI 谱则显示了两个振子带系统,它们是由 Ce 4f16s1 构型的两个能量最低的自旋轨道耦合态电离产生的。这两种 Ln 乙亚胺配合物都是通过氨基在热力学和动力学上有利的协同脱氢反应形成的。Ln(NC2H5) 的另外两种异构体包括由氨基和甲基脱氢形成的四元金属环 Ln(NHCH2CH2),以及由氨基和亚甲基脱氢形成的三元环 Ln(NHCHCH3)。由于在实验条件下不存在环状异构体,因此无法在实验中观察到这些异构体。
{"title":"Spectroscopic and computational characterization of lanthanide-mediated bond activation of ethylamine","authors":"Silver Nyambo,&nbsp;Yuchen Zhang,&nbsp;Dong-Sheng Yang","doi":"10.1016/j.jorganchem.2024.123330","DOIUrl":"10.1016/j.jorganchem.2024.123330","url":null,"abstract":"<div><p>Ln (Ln = La and Ce) atom reactions with ethylamine are conducted in a pulsed laser vaporization supersonic molecular beam source. Dehydrogenation and association metal-containing species are observed with time-of-flight mass spectrometry, and the dehydrogenated Ln ethylimido species in the formula Ln(NC<sub>2</sub>H<sub>5</sub>) are characterized by single-photon mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical calculations. The theoretical calculations include density functional theory for both Ln species and a scalar relativity correction, electron correlation, and spin-orbit coupling through multiconfiguration quasi-degenerate second-order perturbation theory for the Ce species. The MATI spectrum of lanthanum ethylimido La(NCH<sub>2</sub>CH<sub>3</sub>) has a single vibronic band system from the ionization of the doublet ground state with the La 6s<sup>1</sup> configuration, whereas that of the cerium ethylimido Ce(NCH<sub>2</sub>CH<sub>3</sub>) displays two vibronic band system from the ionization of the two lowest-energy spin-orbit coupling states with the Ce 4f<sup>1</sup>6s<sup>1</sup> configuration. Both Ln ethylimido complexes are formed by the thermodynamically and kinetically favorable concerted dehydrogenation of the amino group. Two additional isomers of Ln(NC<sub>2</sub>H<sub>5</sub>) include a four-membered metallacycle Ln(NHCH<sub>2</sub>CH<sub>2</sub>) from the dehydrogenation of the amino and methyl groups and a three-membered cycle Ln(NHCHCH<sub>3</sub>) from the dehydrogenation of the amino and methylene groups. The cyclic isomers are not observed experimentally as they are not populated under the experimental conditions.</p></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1020 ","pages":"Article 123330"},"PeriodicalIF":2.1,"publicationDate":"2024-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142049411","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
Telluropyran and telluropyrylium derivatives, their preparation, and reactivity 碲吡喃和碲吡喃衍生物、其制备和反应性
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-08-18 DOI: 10.1016/j.jorganchem.2024.123327
Mohamed H. Helal , Ateyatallah Aljuhani , Moustafa A. Gouda

Telluropyran and telluropyrylium derivatives are organotellurium compounds featuring a tellurium atom integrated into a pyran or pyrylium ring system. These compounds are of interest due to their unique electronic properties and potential applications in various fields such as materials science, catalysis, and medicine.

When benzene, indene and/or thiophene are fused with the b edge of 4H-telluropyran, four distinct condensed telluropyrans structures can be identified. These include 7H-telluropyrano[3,2-b]thiophene, 4H-tellurochromene, 9H-telluroxanthene and 9-dihydroindeno[2,1-b]telluropyran and 9H-tellurochromeno-[3,2-b]thiophene. The synthesis of telluropyran derivatives is achievable through various chemical pathways, encompassing Suzuki coupling reactions, Stille coupling reactions, and Sonogashira coupling reactions.

碲吡喃和碲芘衍生物是有机碲化合物,其特点是碲原子与吡喃或芘环系统结合在一起。当苯、茚和/或噻吩与 4H-碲吡喃的 b 边融合时,可以发现四种不同的缩合碲吡喃结构。这些结构包括 7H-碲吡喃并[3,2-b]噻吩、4H-碲铬烯、9H-碲氧杂蒽和 9-二氢茚并[2,1-b]碲吡喃以及 9H-碲铬烯并[3,2-b]噻吩。碲吡喃衍生物可通过各种化学途径合成,包括铃木偶联反应、斯蒂尔偶联反应和索诺加希拉偶联反应。
{"title":"Telluropyran and telluropyrylium derivatives, their preparation, and reactivity","authors":"Mohamed H. Helal ,&nbsp;Ateyatallah Aljuhani ,&nbsp;Moustafa A. Gouda","doi":"10.1016/j.jorganchem.2024.123327","DOIUrl":"10.1016/j.jorganchem.2024.123327","url":null,"abstract":"<div><p>Telluropyran and telluropyrylium derivatives are organotellurium compounds featuring a tellurium atom integrated into a pyran or pyrylium ring system. These compounds are of interest due to their unique electronic properties and potential applications in various fields such as materials science, catalysis, and medicine.</p><p>When benzene, indene and/or thiophene are fused with the b edge of 4<em>H</em>-telluropyran, four distinct condensed telluropyrans structures can be identified. These include 7<em>H</em>-telluropyrano[3,2-<em>b</em>]thiophene, 4<em>H</em>-tellurochromene, 9<em>H</em>-telluroxanthene and 9-dihydroindeno[2,1-<em>b</em>]telluropyran and 9<em>H</em>-tellurochromeno-[3,2-<em>b</em>]thiophene. The synthesis of telluropyran derivatives is achievable through various chemical pathways, encompassing Suzuki coupling reactions, Stille coupling reactions, and Sonogashira coupling reactions.</p></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1020 ","pages":"Article 123327"},"PeriodicalIF":2.1,"publicationDate":"2024-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142044790","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
New metallophthalocyanine (M: Ni(II) and Fe(II)) complexes as efficient catalysts for transfer hydrogenation of various ketones 新型金属酞菁(M:Ni(II) 和 Fe(II))配合物作为各种酮转移加氢的高效催化剂
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-08-18 DOI: 10.1016/j.jorganchem.2024.123325
Uğur Işık , Mesut Namlı , Cihan Kantar , Selami Şaşmaz , Murat Aydemir

Hydrogen transfer reduction methods are attracting increasing attention from synthetic chemists in view of their operational simplicity. Therefore, the novel Ni(II) and Fe(II) tetra substituted metallophthalocyanines containing resorcinol and guaiacol groups were synthesized using microwave irradiation and characterized via elemental analysis, UV-Vis and FT-IR spectroscopy, and TGA. The comparison of the catalytic features of phthalocyanine based on metals is discussed in detail. These phthalocyanine-complexes were tested in transfer hydrogenation (TH) of ketones in the existence of KOH, utilizing 2-propanol as a hydrogen source. Examination of different carbonyl substrates revealed that Nickel (II) phthalocyanine, (Ni2) complex was a remarkable catalyst for the catalytic reduction of acetophenones (1.0 mol % of catalyst, 99 % conversion). Furthermore, we have discovered that the catalytic characteristics of this class of molecules are significantly influenced by both steric and electronic variables.

氢转移还原法因其操作简单而日益受到合成化学家的关注。因此,我们利用微波辐照合成了含有间苯二酚和愈创木酚基团的新型 Ni(II) 和 Fe(II) 四取代金属酞菁,并通过元素分析、紫外可见光谱、傅立叶变换红外光谱和热重分析对其进行了表征。详细讨论了基于金属的酞菁催化特性的比较。利用 2-丙醇作为氢源,测试了这些酞菁复合物在 KOH 存在下对酮的转移加氢(TH)反应。对不同羰基底物的研究表明,镍(II)酞菁(Ni2)络合物是催化还原苯乙酮的理想催化剂(催化剂浓度为 1.0 摩尔%,转化率为 99%)。此外,我们还发现这类分子的催化特性受到立体和电子变量的显著影响。
{"title":"New metallophthalocyanine (M: Ni(II) and Fe(II)) complexes as efficient catalysts for transfer hydrogenation of various ketones","authors":"Uğur Işık ,&nbsp;Mesut Namlı ,&nbsp;Cihan Kantar ,&nbsp;Selami Şaşmaz ,&nbsp;Murat Aydemir","doi":"10.1016/j.jorganchem.2024.123325","DOIUrl":"10.1016/j.jorganchem.2024.123325","url":null,"abstract":"<div><p>Hydrogen transfer reduction methods are attracting increasing attention from synthetic chemists in view of their operational simplicity. Therefore, the novel Ni(II) and Fe(II) tetra substituted metallophthalocyanines containing resorcinol and guaiacol groups were synthesized using microwave irradiation and characterized via elemental analysis, UV-Vis and FT-IR spectroscopy, and TGA. The comparison of the catalytic features of phthalocyanine based on metals is discussed in detail. These phthalocyanine-complexes were tested in transfer hydrogenation (TH) of ketones in the existence of KOH, utilizing 2-propanol as a hydrogen source. Examination of different carbonyl substrates revealed that Nickel (II) phthalocyanine, (Ni2) complex was a remarkable catalyst for the catalytic reduction of acetophenones (1.0 mol % of catalyst, 99 % conversion). Furthermore, we have discovered that the catalytic characteristics of this class of molecules are significantly influenced by both steric and electronic variables.</p></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1020 ","pages":"Article 123325"},"PeriodicalIF":2.1,"publicationDate":"2024-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142044791","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
para-Selective C-H Functionalization of Anilines: A Review 苯胺的对位选择性 C-H 功能化:综述
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-08-16 DOI: 10.1016/j.jorganchem.2024.123313
Fatemeh Doraghi , Yasin Mohammadkhani Kalooei , Negar Mehdi Zadeh Darban , Bagher Larijani , Mohammad Mahdavi

Controlling the site-selectivity in the C-H functionalization of anilines is one of the great challenges in synthetic chemistry. Considering the numerous applications of aniline derivatives in pharmaceuticals, agrochemicals and advanced materials, the para-selective functionalization of these scaffolds has received much attention. Various synthetic methods on the para-selective functionalization of primary, secondary and tertiary anilines, including electrophilic aromatic reactions, nucleophilic aromatic reactions, oxidative addition, radical addition, and carbenoid addition are highlighted in this review.

控制苯胺 C-H 功能化的位点选择性是合成化学中的一大挑战。考虑到苯胺衍生物在制药、农用化学品和先进材料中的大量应用,这些支架的副选择官能化受到了广泛关注。本综述重点介绍了有关伯、仲和叔苯胺副选择官能化的各种合成方法,包括亲电芳香反应、亲核芳香反应、氧化加成、自由基加成和类羰基加成。
{"title":"para-Selective C-H Functionalization of Anilines: A Review","authors":"Fatemeh Doraghi ,&nbsp;Yasin Mohammadkhani Kalooei ,&nbsp;Negar Mehdi Zadeh Darban ,&nbsp;Bagher Larijani ,&nbsp;Mohammad Mahdavi","doi":"10.1016/j.jorganchem.2024.123313","DOIUrl":"10.1016/j.jorganchem.2024.123313","url":null,"abstract":"<div><p>Controlling the site-selectivity in the C-H functionalization of anilines is one of the great challenges in synthetic chemistry. Considering the numerous applications of aniline derivatives in pharmaceuticals, agrochemicals and advanced materials, the <em>para</em>-selective functionalization of these scaffolds has received much attention. Various synthetic methods on the <em>para</em>-selective functionalization of primary, secondary and tertiary anilines, including electrophilic aromatic reactions, nucleophilic aromatic reactions, oxidative addition, radical addition, and carbenoid addition are highlighted in this review.</p></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1019 ","pages":"Article 123313"},"PeriodicalIF":2.1,"publicationDate":"2024-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142006935","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
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Journal of Organometallic Chemistry
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