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Synthesis and structural characterization of Ti(III) and Mo(III) complexes supported by PNP pincer ligands PNP钳形配体负载Ti(III)和Mo(III)配合物的合成及结构表征
Pub Date : 2023-09-30 DOI: 10.5155/eurjchem.14.3.311-315.2463
Rita Ruivo, Luis Alves, Ana Martins
New Ti(III) and Mo(III) complexes of formulae [(PNP-Ph)TiCl3], 1, and [(PNP-iPr)MoCl3], 2, where PNP-Ph = N,N’-bis(diphenylphosphino)-2,6-diaminopyridine and PNP-iPr = N,N’-bis(diisopropylphosphino)-2,6-diaminopyridine were synthesised, in moderate yields, by reaction of MCl3·(THF)3 (M = Ti and Mo) with the suitable ligand precursor. The solid-state molecular structures of complexes 1 and 2 were obtained by single-crystal X-ray diffraction. Crystal data for C37H41Cl3N3O2P2Ti (1·(C4H8O)2): triclinic, space group P-1 (no. 2), a = 10.0945(4) Å, b = 10.3002(4) Å, c = 18.6233(7) Å, α = 92.412(2)°, β = 91.108(2)°, γ = 101.705(3)°, V = 1893.65(13) Å3, Z = 2, µ(MoKα) = 0.559 mm-1, Dcalc = 1.361 g.cm-3, 20760 reflections measured (2.021 ≤ Θ ≤ 27.130), 8327 unique (Rint = 0.0399, Rsigma = 0.0414) which were used in all calculations. The final R1 was 0.0316 (I > σ(I)) and wR2 was 0.0850 (all data). Crystal data for C17H33Cl3MoN3P2 (2): tetragonal, space group I41/a (no. 88), a = b = 19.468(4) Å, c = 31.711(6) Å, α = β = γ = 90°, V = 12019(5) Å3, Z = 16, µ(MoKα) = 0.816 mm-1, Dcalc = 1.202 g.cm-3, 42367 reflections measured (2.569 ≤ Θ ≤ 25.347), 5498 unique (Rint = 0.1408, Rsigma = 0.1293) which were used in all calculations. The final R1 was 0.1005 (I > σ(I)) and wR2 was 0.3194 (all data). The coordination geometry around the titanium and molybdenum centers is best described as octahedral, with three donor atoms of the PNP ligand and one chlorine atom occupying the equatorial plane. The axial positions of the octahedron are occupied by the other two chlorido ligands in both complexes. The NH spacer groups in the PNP ligands have an important role in the establishment of hydrogen bonds between the complexes and molecules of the solvent or neighbouring species.
通过MCl3·(THF)3 (M = Ti和Mo)与合适的配体前体反应,以中等产率合成了新的[(PNP-Ph)TiCl3], 1和[(PNP-iPr)MoCl3], 2式Ti(III)和Mo(III)配合物,其中PNP-Ph = N,N′-双(二苯基膦)-2,6-二氨基吡啶和PNP-iPr = N,N′-双(二异丙基膦)-2,6-二氨基吡啶。通过单晶x射线衍射得到了配合物1和2的固态分子结构。C37H41Cl3N3O2P2Ti(1·(c4h80)2)晶体数据:三斜,空间群P-1 (no.;2), a = 10.0945(4) Å, b = 10.3002(4) Å, c = 18.6233(7) Å, α = 92.412(2)°,β = 91.108(2)°,γ = 101.705(3)°,V = 1893.65(13) Å3, Z = 2,µ(MoKα) = 0.559 mm-1, Dcalc = 1.361 g.cm-3,测量反射(2.021≤Θ≤27.130)20760个,unique (Rint = 0.0399, Rsigma = 0.0414) 8327个,用于所有计算。最终R1为0.0316 (I >σ(I)), wR2为0.0850(所有数据)。C17H33Cl3MoN3P2(2)的晶体数据:四边形,空间群I41/a (no. 2);a = b = 19.468(4) Å, c = 31.711(6) Å, α = β = γ = 90°,V = 12019(5) Å3, Z = 16,µ(MoKα) = 0.816 mm-1, Dcalc = 1.202 g.cm-3, 42367个反射测量值(2.569≤Θ≤25.347),5498个unique (Rint = 0.1408, Rsigma = 0.1293)用于所有计算。最终R1为0.1005 (I >σ(I)), wR2为0.3194(所有数据)。钛和钼中心周围的配位几何结构最好描述为八面体,PNP配体的三个给体原子和一个氯原子占据赤道面。在这两个配合物中,八面体的轴向位置被另外两个氯基配体占据。PNP配体中的NH间隔基团在配合物与溶剂或邻近物质分子之间建立氢键方面起着重要作用。
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引用次数: 0
Green synthesis of silver nano-catalyst using ionic liquid and their photocatalytic application to the reduction of p-nitrophenol 离子液体绿色合成纳米银催化剂及其光催化还原对硝基苯酚的应用
Pub Date : 2023-09-30 DOI: 10.5155/eurjchem.14.3.316-322.2436
Ravi Ranjan, Durga Gupta, Madhulata Shukla
Ionic liquids (ILs) carrying special properties can act as electronic as well as steric stabilisers by preventing nanoparticle (NP) growth and NP aggregation. The effect of visible light on the catalytic properties of silver nanoparticles is a hot topic of extensive research nowadays. The present report demonstrates the current developments in the green synthesis of silver nanoparticles in ionic liquids and a detailed study of the room-temperature catalytic and photocatalytic reduction of p-nitrophenol (PNP) to p-aminophenol (AP). The Ag nanoparticles (AgNPs) functionalised by ionic liquids are prepared in the 40-140 nm range and are found to be spherical in shape. The photocatalytic properties of these nanocomposites for the reduction of PNP to AP were studied. Photocatalytic degradation of PNP was also analysed by these composite nanostructures. The plasmonic photocatalytic properties of the synthesised AgNPs revealed activity significantly higher than that of the room-temperature catalysis. Density functional theory calculations showed that strong interactions exist between nanoclusters and ILs. Natural bond orbital analysis showed that IL also activates the nanoparticles for further photocatalytic reduction by transferring electron transfer from the donor (IL) to the acceptor (Ag cluster) and activating the silver NPs for further catalytic reaction. Photocatalytic degradation of PNP (reduction of PNP to AP) using NP in the absence of light follows first-order kinetics, whereas in the presence of light it follows zero-order reaction kinetics.
携带特殊性质的离子液体(ILs)可以通过阻止纳米颗粒(NP)的生长和聚集而起到电子和空间稳定剂的作用。可见光对纳米银催化性能的影响是目前广泛研究的热点问题。本报告阐述了离子液体中纳米银绿色合成的最新进展,并详细研究了对硝基酚(PNP)在室温和光催化下还原为对氨基酚(AP)的过程。离子液体功能化的银纳米颗粒(AgNPs)在40-140 nm范围内被制备,并且发现其形状为球形。研究了这些纳米复合材料将PNP还原为AP的光催化性能。研究了复合纳米结构对PNP的光催化降解作用。所合成的AgNPs的等离子体光催化活性明显高于室温催化活性。密度泛函理论计算表明,纳米团簇与il之间存在强相互作用。自然键轨道分析表明,IL还通过将电子从供体(IL)转移到受体(Ag簇)并激活银NPs进行进一步的催化反应,从而激活纳米粒子进行进一步的光催化还原。在没有光的情况下,使用NP光催化降解PNP(将PNP还原为AP)遵循一级动力学,而在有光的情况下,它遵循零级反应动力学。
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引用次数: 0
Study of expired Fuclo 500 drug as an environmentally sustainable corrosion inhibitor 过期药物Fuclo 500作为环境可持续缓蚀剂的研究
Pub Date : 2023-09-30 DOI: 10.5155/eurjchem.14.3.353-361.2443
Aphouet Aurelie Koffi, N'guadi Blaise Allou, Mougo Andre Tigori, Teminfolo Yaya Soro, Albert Trokourey, Paulin Marius Niamien
This work deals with aluminium corrosion inhibition by expired drugs containing flucloxacillin in 1 M hydrochloric acid medium, using the gravimetric method and density functional theory. Weight loss results showed that the inhibitory efficiency of this compound increases with concentration and decreases with increasing temperature. The study also indicates that this molecule is adsorbed according to the modified Langmuir model (Villamil model). Furthermore, the thermodynamic parameters of adsorption (∆Goads, ∆Hoads, ∆Soads) and activation (Ea*, ΔHa*, ΔSa*) show that the adsorption is mixed type (chemisorption and physisorption). In addition, density functional theory provides access to the quantum chemical parameters of the molecule such as the lowest vacant orbital energy (ELUMO), the highest occupied orbital energy (EHOMO), the absolute electronegativity (χ), the global hardness (η), the global softness (S), the fraction of transferred electrons (ΔN) as well as the electrophilicity index (ω) for finding correlation between the inhibitor structure and the experimental data.
采用重量法和密度泛函理论研究含氟氯西林过期药物在1 M盐酸介质中对铝的缓蚀作用。减重结果表明,该化合物的抑菌效果随浓度的增加而增加,随温度的升高而降低。研究还表明,该分子的吸附符合修正的Langmuir模型(Villamil模型)。吸附(∆Goads,∆Hoads,∆Soads)和活化(Ea*, ΔHa*, ΔSa*)的热力学参数表明,吸附为混合型(化学吸附和物理吸附)。此外,密度泛函数理论还提供了分子的量子化学参数,如最低空轨道能(ELUMO)、最高已占轨道能(EHOMO)、绝对电负性(χ)、整体硬度(η)、整体柔软度(S)、转移电子分数(ΔN)以及亲电性指数(ω),用于寻找抑制剂结构与实验数据之间的相关性。
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引用次数: 0
From ancient Asian relics to contemporaneity: A review of historical and chemical aspects of Cannabis 从古代亚洲遗迹到当代:大麻的历史和化学方面的回顾
Pub Date : 2023-09-30 DOI: 10.5155/eurjchem.14.3.393-400.2442
Gabriel Vitor de Lima Marques, Renata Barbosa de Oliveira
From the Himalayan mountains to the South American coast, Cannabis, a general term for plants of the genus Cannabis, with thousands of years of contact with humankind, shows its versatility as food tools such as hemp, religious and hedonistic input, and other purposes through the millennia, according to the populations in question. In this paper, a review of the context of the use of Cannabis and its place in world history is presented, from ancient Mesopotamian relics, traditional Chinese and Ayurvedic medicines, to the reasoning behind the isolation and structural elucidation of three phytocannabinoids and the spread of Cannabis throughout the world.
从喜马拉雅山脉到南美海岸,大麻是大麻属植物的总称,与人类接触了数千年,根据所讨论的人口,大麻显示出其作为食物工具(如大麻),宗教和享乐投入以及其他用途的多功能性。在本文中,回顾了大麻的使用背景及其在世界历史上的地位,从古代美索不达米亚遗迹,传统的中国和阿育吠陀药物,到三种植物大麻素的分离和结构解释背后的原因以及大麻在世界各地的传播。
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引用次数: 0
Green synthesis of gold nanoparticles using Sambucus ebulus fruit extract, characterization, and antileishmanial, antibacterial, antioxidant, and photocatalytic activities 绿色金纳米颗粒的合成利用山楂果实提取物,表征,抗利什曼原虫,抗菌,抗氧化,和光催化活性
Pub Date : 2023-06-30 DOI: 10.5155/eurjchem.14.2.223-230.2403
Mohammad Ali Ebrahimzadeh, Seyedeh Roya Alizadeh, Zahra Hashemi
In this study, gold nanoparticles were synthesized using the fruit extract of Sambucus ebulus (S. ebulus) as a reducing, capping, and stabilizing agent. Biogenic synthesis of gold nanoparticles (Au nanoparticles) was accomplished using S. ebulus fruit extract in the presence of hydrogen tetrachloroaurate(III) trihydrate at a temperature of 65 °C and the solution stirred at 400 rpm. The characterization of the synthesized nanoparticles (SE-AuNPs) was performed using different analytical methods, such as scanning electron microscopy (FE-SEM), energy dispersion X-ray spectroscopy (EDS), Fourier transform infrared (FT-IR), X-ray diffraction analysis (XRD), and UV-vis spectroscopy. A strong absorption peak at 565 nm confirmed the formation of the gold nanoparticle. On the basis of the electron microscopy results, AuNPs were mostly spherical with an average size of 116.2 nm. The cubic crystalline structure of the prepared nanoparticles was confirmed using the XRD pattern and the average crystallite size was obtained at 28.471 nm. FT-IR analysis confirmed the presence of functional groups in the plant extract for the synthesis of nanoparticles. SE-AuNPs showed good antibacterial activity against Gram-positive and Gram-negative bacteria tested and exhibited potent antileishmanial activity. Furthermore, SE-AuNPs showed excellent antioxidant activity that inhibited DPPH radicals with an IC50 value of 21.976 µg/mL. The prepared AuNPs acted to degrade methyl orange (MO), which was performed in sodium borohydride and visible light.
在这项研究中,金纳米颗粒的合成是由Sambucus ebulus (S. ebulus)果实提取物作为还原,封盖和稳定剂。在四氯酸氢(III)三水合物存在下,在65°C的温度下,以400转/分的转速搅拌,利用S. ebulus果提取物完成了金纳米颗粒(Au纳米颗粒)的生物合成。采用扫描电镜(FE-SEM)、能量色散x射线能谱(EDS)、傅里叶变换红外(FT-IR)、x射线衍射分析(XRD)和紫外可见光谱等分析方法对合成的SE-AuNPs进行了表征。565 nm处的强吸收峰证实了金纳米颗粒的形成。电镜结果显示,AuNPs多为球形,平均尺寸为116.2 nm。用XRD谱图证实了所制备纳米颗粒的立方晶结构,平均晶粒尺寸为28.471 nm。FT-IR分析证实了植物提取物中存在用于纳米颗粒合成的官能团。SE-AuNPs对革兰氏阳性菌和革兰氏阴性菌均表现出良好的抗菌活性,并表现出较强的抗利什曼原虫活性。SE-AuNPs具有良好的抗氧化活性,其IC50值为21.976µg/mL。制备的AuNPs在硼氢化钠和可见光条件下降解甲基橙(MO)。
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引用次数: 0
Graphical Contents 图形化内容
Pub Date : 2023-06-30 DOI: 10.5155/eurjchem.14.2.iii-vii.2441
Hakan Arslan
Graphical Contents
图形化内容
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引用次数: 0
Graphical Contents 图形化内容
Pub Date : 2023-03-31 DOI: 10.5155/eurjchem.14.1.iii-vii.2430
Hakan Arslan
Graphical Contents
图形化内容
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引用次数: 0
A corrected benzene nitration three-step mechanism derived by DFT calculation and MO theory 通过DFT计算和MO理论推导了苯硝化反应的修正三步反应机理
Pub Date : 2023-03-31 DOI: 10.5155/eurjchem.14.1.39-52.2340
Hongchang Shi
Density-functional theory (DFT) calculations at the LC-wHPBE/6-311++G(d,p) level found that the textbook three-step nitration mechanism of benzene in mixed acids was seriously wrong. Step 1 of generating nitronium ion (NO2+) is not spontaneous, the NO2+ is generated by Lewis collision, and needs to overcome a barrier Ea = 18 or 22 kcal/mol in mixed acid or in nitric acid. Obtaining the Ea of the Lewis collision by quantum chemical calculations is a highlight of the study. The reaction system (NO2+ + H2O) + HSO4⎺ or + NO3⎺ or + nH2O (n ≥ 1) can make NO2+ spontaneously change to HNO3 through a poly(≥3)-molecular acidification. Sulfuric acid can greatly reduce [H2O] and increase [NO2+]. Therefore, the nitration rate in mixed acid is much faster than that in nitric acid. Step 2, C6H6 + NO2+, is an electrophilic addition, follows the transition state theory, and needs to overcome a low barrier, ΔE* = 7 kcal/mol. The product of Step 2 is the σ-complex C6H6-NO2+. The essence of the electrophilic addition is the transfer of HOMO-1 electrons of C6H6 to LUMO of NO2+. Step 3 is a spontaneous Lewis acid-base neutralization without any barrier, and generates the target product nitrobenzene C6H5NO2. NO2+ and σ-complex are the two active intermediates in nitration. The benzene nitration rate control step is not Step 2 of generating σ-complex, but is Step 1 to generate NO2+. The DFT calculation obtains the barriers Ea and ΔE*, the reaction heats ΔHσ and ΔHp of each step of the nitration, resulting in the total nitration reaction heat ΔH = -35 kcal/mol. It is consistent with the experimental ΔH = -34 kcal/mol. Based on the results, a corrected benzene nitration three-step mechanism proposed.
LC-wHPBE/6-311++G(d,p)水平的密度泛函理论(DFT)计算发现,教科书中苯在混合酸中的三步硝化机理存在严重错误。生成氮离子(NO2+)的第1步不是自发的,NO2+是由Lewis碰撞产生的,需要克服混合酸或硝酸中Ea = 18或22 kcal/mol的势垒。利用量子化学计算获得刘易斯碰撞的Ea是本研究的一个重点。反应体系(NO2+ + H2O) + HSO4⎺或+ NO3⎺或+ nH2O (n≥1)可通过聚(≥3)分子酸化使NO2+自发转化为HNO3。硫酸能使[H2O]大幅度还原,[NO2+]大幅度增加。因此,在混合酸中的硝化速度比在硝酸中的硝化速度快得多。第二步,C6H6 + NO2+是亲电加成,遵循过渡态理论,需要克服一个低势垒,ΔE* = 7 kcal/mol。第二步的产物是σ-络合物C6H6-NO2+。亲电加成的实质是C6H6的HOMO-1电子向NO2+的LUMO转移。步骤3为无屏障自发Lewis酸碱中和反应,生成目标产物硝基苯C6H5NO2。NO2+和σ-络合物是硝化反应的活性中间体。苯硝化速率控制步骤不是生成σ-络合物的步骤2,而是生成NO2+的步骤1。通过DFT计算得到各步硝化反应的势垒Ea和ΔE*,反应热量ΔHσ和ΔHp,得到总硝化反应热量ΔH = -35 kcal/mol。与实验结果ΔH = -34 kcal/mol一致。在此基础上,提出了修正的苯硝化三步反应机理。
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引用次数: 1
期刊
European Journal of Chemistry
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