Inorganica Chimica Acta最新文献_第3页

Enhancing formate yield through electrochemical CO2 reduction using BiOCl and g-C3N4 hybrid catalyst 使用 BiOCl 和 g-C3N4 混合催化剂通过电化学二氧化碳还原提高甲酸酯产量

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2024-09-26 DOI: 10.1016/j.ica.2024.122395

Electrochemical carbon dioxide (CO₂) reduction with bismuth-based catalysts has been widely investigated in the recent few years. This is due to bismuth’s ability to perform selective electrochemical CO₂ reduction reaction (eCO₂RR) to an important C₁ product, the formate (HCOO^–). However, boosting the performance of such catalysts is a continuous investigation. In this work, enhancing the active sites for eCO₂RR is investigated by forming nanocomposites with graphitic carbon nitride (g-C₃N₄). BiOCl is synthesized by a simple wet-chemical approach in the presence of glycine as size-controlling agent and formed into nanocomposites, which were characterized by Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), Infrared (IR) Spectroscopy and N₂ physisorption. Linear Sweep Voltammetry (LSV) in argon and CO₂-saturated atmosphere showed higher current values in the case of CO₂. Chronoamperometries (CA) were recorded at −1.06 V vs Reversible Hydrogen Electrode (RHE) for 5400 s obtaining Faradic Efficiencies (FE) varying in the range of 70–77 % depending on the nanocomposites’ composition. In fact, 52.1 wt% BiOCl/g-C₃N₄ formed the highest yields for formate (with also the highest rate of formation of formate) together with a minimal production of H₂ and CO. The effect of nano-structuration induced by glycine, used as a size-controlling agent, to form nanoplates was crucial: microplates of BiOCl produced without glycine showed an FE of 4 %, reaching 85 % in the case of the nanoplates. Post-electrocatalysis characterization revealed the possible role of Bi₂O₂CO₃ as the active phase for eCO₂RR.

近年来，使用铋基催化剂进行电化学二氧化碳（CO2）还原反应的研究十分广泛。这是因为铋能够进行选择性电化学二氧化碳还原反应（eCO2RR），生成重要的 C1 产物--甲酸（HCOO-）。然而，提高此类催化剂的性能是一项持续的研究。在这项工作中，研究人员通过与氮化石墨碳（g-C3N4）形成纳米复合材料来增强 eCO2RR 的活性位点。在甘氨酸作为尺寸控制剂的存在下，通过简单的湿化学方法合成了 BiOCl，并将其制成纳米复合材料，通过扫描电子显微镜 (SEM)、X 射线衍射 (XRD)、拉曼光谱、X 射线光电子能谱 (XPS)、红外 (IR) 光谱和 N2 物理吸附对其进行了表征。氩气和二氧化碳饱和气氛下的线性扫描伏安法（LSV）显示，二氧化碳的电流值更高。根据纳米复合材料的成分，在-1.06 V 与可逆氢电极（RHE）的电压下记录了 5400 秒的计时器（CA），得到的法拉第效率（FE）在 70-77 % 的范围内变化。事实上，52.1 wt% 的 BiOCl/g-C3N4 形成的甲酸盐产量最高（甲酸盐的形成率也最高），同时产生的 H2 和 CO 极少。甘氨酸（用作尺寸控制剂）诱导的纳米结构化对形成纳米板的影响至关重要：在不使用甘氨酸的情况下生产的微板 BiOCl 的 FE 为 4%，而在使用纳米板的情况下则达到 85%。电催化后表征显示，Bi2O2CO3 可能是 eCO2RR 的活性相。

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引用次数: 0

Heteroleptic complexes of hydrazone Scaffold of picolinoyl N- oxide and 2,4 dihydroxy phenyl moieties; evaluation of antioxidant activity, DNA and protein binding properties and in vitro antiproliferation studies 吡啶酮 N-氧化物和 2,4 二羟基苯基的腙支架异性复合物；抗氧化活性、DNA 和蛋白质结合特性的评估以及体外抗增殖研究

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2024-09-26 DOI: 10.1016/j.ica.2024.122391

The present study deals with design and synthesis of new mononuclear Cu(II), Co(II), Ni(II) and Zn(II) metal complexes of hydrazone of 2-(2-(2,4-dihydroxybenzylidene)hydrazinecarbonyl)pyridine-1-oxide (H₂L), in a view to study their potential relevance for the biological applications. Structural aspects of the title compound (H₂L) and metal complexes synthesized were evaluated by spectral and analytical methods viz. ¹H NMR, ¹³C NMR, LC-MS, FT-IR, UV–Visible, SEM, EDX, Powder XRD, ESR, TGA and DTA. Ligational properties of H₂L were explored by employing pH metric equilibrium studies for recognizing metal ion binding potential donor sites, and further HyperChem 7.5 software for computing properties of frontier molecular orbitals to ascertain orientation of highest occupied molecular orbitals from which presumably electrons are donated to metal ion in complex formation. The affinity of all title compounds to bind with CT-DNA and the type of interaction, therein have been studied by conducting UV–VIS absorption and fluorescence emission titrations. The protein-binding ability of all metal complexes with two serum proteins (BSA and HSA) were explored by absorption titrations, and further fluorescence titrations for BSA binding were also performed. Antioxidant activity of the title compounds was carried out by the method of free radical scavenging using spectrophotometric technique. Additionally, cytotoxicity of all metal complexes and ligand was measured by CTG cell proliferation assay after treating them with MDA-MB-231 and SKOV-3 cell lines. The cell cycle arrest and apoptosis assay in above cell lines after treatment with title compounds were also investigated by flow cytometry. In addition, molecular docking studies at target CDK2 protein inferred binding affinity of the title compounds through non covalent bonding interactions.

本研究涉及 2-(2-(2,4-二羟基亚苄基)肼羰基)吡啶-1-氧化物 (H2L) 的腙的新单核 Cu(II)、Co(II)、Ni(II) 和 Zn(II)金属配合物的设计与合成，以期研究它们在生物应用中的潜在相关性。通过光谱和分析方法，即 1H NMR、13C NMR、LC-MS、FT-IR、UV-Visible、SEM、EDX、粉末 XRD、ESR、TGA 和 DTA，对标题化合物（H2L）和合成的金属配合物的结构进行了评估。通过使用 pH 指标平衡研究来识别金属离子结合的潜在供体位点，并进一步使用 HyperChem 7.5 软件计算前沿分子轨道的特性，以确定最高占位分子轨道的取向，从而推测在形成络合物时，电子会从这些轨道捐献给金属离子，从而探索 H2L 的配位特性。通过紫外可见吸收和荧光发射滴定法，研究了所有标题化合物与 CT-DNA 结合的亲和力及其相互作用的类型。通过吸收滴定法研究了所有金属复合物与两种血清蛋白（BSA 和 HSA）的蛋白质结合能力，并进一步进行了 BSA 结合的荧光滴定。标题化合物的抗氧化活性是通过分光光度法清除自由基的方法得出的。此外，所有金属复合物和配体在处理 MDA-MB-231 和 SKOV-3 细胞系后，都通过 CTG 细胞增殖试验测定了细胞毒性。流式细胞仪还检测了用标题化合物处理上述细胞系后细胞周期停滞和凋亡的情况。此外，对目标 CDK2 蛋白进行的分子对接研究推断出了标题化合物通过非共价键相互作用而产生的结合亲和力。

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引用次数: 0

Green synthesis and antimicrobial evaluation of Ag/TiO2 and Ag/SeO2 Core-Shell nanocomposites using r. Officinalis extract: A combined experimental and docking study 利用R.O. Officinalis提取物绿色合成Ag/TiO2和Ag/SeO2核壳纳米复合材料并对其进行抗菌评价：实验与对接的综合研究提取物的 Ag/TiO2 和 Ag/SeO2 芯壳纳米复合材料的绿色合成与抗菌评价：实验与对接的综合研究

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2024-09-24 DOI: 10.1016/j.ica.2024.122390

The escalating threat of antibiotic resistance necessitates the development of novel, sustainable antibacterial agents. This study investigates the potential of utilizing Rosmarinus officinalis leaf extracts to synthesize Ag/TiO₂ and Ag/SeO₂ nanocomposites. R. officinalis extract, a rich source of phenolic and flavonoid compounds, effectively and safely acts as a reducing and capping agent for the green synthesis of Ag/TiO₂ and Ag/SeO₂ nanocomposites. Characterization of nanocomposites revealed the nanoparticles’ nanoscale size, ranging from 43.34 to 96.58 nm for Ag/TiO₂ and 8.04 to 21.72 nm for Ag/SeO₂. Both types of nanoparticles exhibited a spherical morphology and distinct crystalline structure. The nanoparticles demonstrated significant antibacterial properties against multiple bacterial strains. The effective concentration for antibacterial activity was determined to be 30.99 mg/mL for Ag-TiO₂ and 32.41 mg/mL for Ag-SeO₂ nanoparticles. The surface charge of the nanoparticles was measured to be −14.0 mV for Ag-TiO₂ and −15.4 mV for Ag/SeO₂. Molecular docking simulations investigated the interactions between rosmarinic acid, its derivatives, and the antibiotic cefotaxime with a bacterial protein (e.g., DNA gyrase). These simulations provided insights into the distinct antibacterial mechanisms of these compounds. Briefly, this research highlights the potential of R. officinalis-derived nanocomposites as promising antibacterial agents. The eco-friendly synthesis and promising results pave the way for their development and application in medicine, biochemistry, and environmental fields.

抗生素耐药性的威胁不断升级，因此有必要开发新型、可持续的抗菌剂。本研究探讨了利用迷迭香叶提取物合成 Ag/TiO2 和 Ag/SeO2 纳米复合材料的潜力。蔷薇叶提取物是酚类和类黄酮化合物的丰富来源，可有效、安全地用作还原剂和封端剂，用于 Ag/TiO2 和 Ag/SeO2 纳米复合材料的绿色合成。纳米复合材料的表征显示，Ag/TiO2 和 Ag/SeO2 纳米粒子的尺寸分别为 43.34 纳米至 96.58 纳米和 8.04 纳米至 21.72 纳米。两种纳米粒子都呈现球形形态和独特的晶体结构。纳米粒子对多种细菌菌株具有显著的抗菌特性。经测定，Ag-TiO2 和 Ag-SeO2 纳米粒子的有效抗菌浓度分别为 30.99 毫克/毫升和 32.41 毫克/毫升。经测量，Ag-TiO2 纳米粒子的表面电荷为-14.0 mV，Ag/SeO2 纳米粒子的表面电荷为-15.4 mV。分子对接模拟研究了迷迭香酸、其衍生物和抗生素头孢他啶与细菌蛋白质（如 DNA 回旋酶）之间的相互作用。这些模拟深入揭示了这些化合物的不同抗菌机制。简而言之，这项研究凸显了茜草提取的纳米复合材料作为抗菌剂的潜力。环保的合成方法和良好的结果为其在医学、生物化学和环境领域的开发和应用铺平了道路。

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引用次数: 0

Organotin carboxylates with bulky substituents. Synthesis, structure, cytotoxicity and antioxidant activity 具有笨重取代基的有机锡羧酸盐。合成、结构、细胞毒性和抗氧化活性

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2024-09-24 DOI: 10.1016/j.ica.2024.122388

A series of organotin carboxylates were synthesized and characterized by NMR (¹H, ¹³C, ¹¹⁹Sn) and IR spectroscopy, ESI mass-spectrometry and elemental analysis. The structure of two compounds was resolved directly using X-ray diffraction analysis and unusual heptacoordinated Sn coordination polyhedron was discovered for them. Antioxidant activity of the synthesized compounds was estimated using DPPH, NBT and CUPRAC-tests, lipid peroxidation and lipoxygenase inhibition capacity as well. It was shown that the presence of the hydroxyl group in the aromatic ring of the ligand drastically increases antioxidant potency of the complexes, while not noticeably affecting the antiproliferative properties, which were measured with the standard MTT-test. Moreover, it was shown that derivatives of dibutyl- and di-tert-butyltin exhibit the highest cytotoxicity. Three complexes were put forward as lead compounds and additional apoptosis induction studies were carried out. Noticeable caspase activation was shown for the complexes 4 and 7 thus marking their mode of action. The results obtained show that the complexes herein described are promising antiproliferative agents.

合成了一系列有机锡羧酸盐，并通过核磁共振（1H、13C、119Sn）和红外光谱、ESI 质谱和元素分析对其进行了表征。利用 X 射线衍射分析直接解析了两种化合物的结构，并发现了它们不同寻常的七配位 Sn 配位多面体。利用 DPPH、NBT 和 CUPRAC 测试、脂质过氧化和脂氧合酶抑制能力评估了合成化合物的抗氧化活性。结果表明，配体芳香环中羟基的存在极大地提高了复合物的抗氧化能力，但对抗增殖特性的影响并不明显，抗增殖特性是通过标准的 MTT 试验测定的。此外，研究表明二丁基锡和二叔丁基锡的衍生物具有最高的细胞毒性。研究人员将三种复合物作为先导化合物，并进行了更多的细胞凋亡诱导研究。复合物 4 和 7 显示出明显的 caspase 激活作用，从而确定了它们的作用模式。研究结果表明，上述复合物是很有前途的抗增殖剂。

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引用次数: 0

Revealing the Unusual behavior of rhenium (I) tricarbonyl complex functionalized with Aza-Macrocycles in response to metal ions 揭示氮杂环三羰基铼 (I) 复合物在金属离子作用下的异常行为

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2024-09-24 DOI: 10.1016/j.ica.2024.122389

Three new rhenium phenanthroline tricarbonyl complexes were synthesized and fully characterized to examine changes in their photophysical properties and spectroscopic behavior in the presence of metal ions. To achieve this, the complexes were designed with modifications in both the phenanthroline and the axial ligand. The 4,7–dichloro–1,10–phenanthroline (Cl₂phen) precursor was functionalized with two units of 1–aza–15–crown–5 (1A15C5) to obtain the complex [Re((A15C5)₂phen)(CO)₃Br] (1) with the aim to study the spectroscopic perturbations induced by the binding of the metal ions by this receptor. Interestingly, the rhenium complex 1 shows a particular behavior towards Hg(II) and Pb(II), as a result of the halide abstraction assisted by these metal ions. Additionally, in the presence of Cu(II) the interaction and coordination/binding with the macrocycle cavities is also presumed. The chemical reaction assisted by Hg(II) was confirmed by changes in the absorption, emission and FT–IR spectra of [Re(Cl₂phen)(CO)₃Br] (2) in presence of the heavy metal ion. These obtained profiles had similar patterns to the ones shown by the cationic complex [Re(Cl₂phen)(CO)₃(CH₃CN)]PF₆ (3). As final confirmation, this last complex was also studied in the presence of metal ions and its spectra remained unaltered.

我们合成了三种新的菲罗啉三羰基铼配合物，并对其进行了全面表征，以研究它们在金属离子存在下的光物理特性和光谱行为的变化。为此，在设计配合物时对菲罗啉和轴向配体都进行了修改。将 4,7-二氯-1,10-菲罗啉（Cl2phen）前体与两个单位的 1-氮杂-15-冠-5（1A15C5）进行官能化，得到了[Re((A15C5)2phen)(CO)3Br] 复合物（1），目的是研究金属离子与该受体结合时引起的光谱扰动。有趣的是，铼络合物 1 对 Hg(II) 和 Pb(II) 显示出特殊的行为，这是这些金属离子协助卤化物抽取的结果。此外，在 Cu（II）存在的情况下，还可以推测与大循环空腔发生了相互作用和配位/结合。重金属离子存在时，[Re(Cl2phen)(CO)3Br] (2) 的吸收、发射和傅立叶变换红外光谱的变化证实了 Hg(II) 的化学反应。这些光谱曲线与阳离子络合物 [Re(Cl2phen)(CO)3(CH3CN)]PF6 (3) 的光谱曲线相似。作为最后的确认，我们还在有金属离子存在的情况下研究了最后一种复合物，其光谱保持不变。

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引用次数: 0

Effect of solution environment on the binding properties of ruthenium(II) complexes [Ru(bim)2(7-CH3-dppz)]2+ and [Ru(bim)2(dppx)]2+ with double-stranded RNA poly(A)·poly(U) 溶液环境对钌(II)配合物[Ru(bim)2(7-CH3-dppz)]2+和[Ru(bim)2(dppx)]2+与双链 RNA 聚(A)-聚(U)结合特性的影响

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2024-09-24 DOI: 10.1016/j.ica.2024.122387

Two new ruthenium(Ⅱ) complexes containing the same ancillary ligands and different intercalating ligands, [Ru(bim)₂(7-CH₃-dppz)]²⁺ (Ru1, bim = 2,2′-biimidazole, 7-CH₃-dppz = 7-methyl-dipyrido-[3,2-a,2′,3′-c]-phenazine) and [Ru(bim)₂(dppx)]²⁺ (Ru2, dppx = 7,8-dimethyldipyridophenazine), have been synthesized and characterized in this work, and the interactions of Ru1 and Ru2 with double-stranded RNA poly(A)·poly(U) have been comparatively studied under both dilute and molecular crowding conditions. Analysis of spectral titrations and viscosity experiments as well as thermal denaturation experiments suggests that although complexes Ru1 and Ru2 in both dilute and molecular crowding solutions bind to poly(A)·poly(U) via intercalation, while the binding and stabilizing effects of the two complexes toward poly(A)·poly(U) under molecular crowding conditions significantly decreases in comparision with those in dilute solutions, suggesting that molecular crowding has a significant weakening effect on the interaction of the two complexes with poly(A)-poly(U). The results obtained will contribute to the understanding of the effects of molecular crowding conditions on the binding and stabilization of double-stranded RNA by metal complexes, in particular Ru(II) complexes.

含有相同辅助配体和不同插层配体的两种新钌（Ⅱ）配合物 [Ru(bim)2(7-CH3-dppz)]2+ （Ru1、bim = 2,2′-双咪唑，7-CH3-dppz = 7-甲基-二吡啶-[3,2-a,2′,3′-c]-吩嗪）和 [Ru(bim)2(dppx)]2+ （Ru2、dppx = 7,8-二甲基二哒嗪），并比较研究了 Ru1 和 Ru2 在稀释和分子拥挤条件下与双链 RNA 聚（A）-聚（U）的相互作用。光谱滴定和粘度实验以及热变性实验的分析表明，虽然 Ru1 和 Ru2 复合物在稀溶液和分子挤入溶液中都是通过插层作用与聚(A)-聚(U)结合的，但这两种复合物在分子挤入条件下对聚(A)-聚(U)的结合和稳定作用比在稀溶液中明显降低，表明分子挤入对这两种复合物与聚(A)-聚(U)的相互作用有明显的削弱作用。研究结果将有助于理解分子拥挤条件对金属配合物（尤其是 Ru(II) 配合物）结合和稳定双链 RNA 的影响。

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引用次数: 0

Adenosine triphosphatase synergetic cobalt metal-organic frameworks with enhanced peroxidase-like activity for L-cystine detection 具有增强过氧化物酶样活性的腺苷三磷酸酶协同钴金属有机框架，用于检测 L-胱氨酸

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2024-09-21 DOI: 10.1016/j.ica.2024.122375

The role of metal–organic frameworks (MOFs) in the field of enzyme-like materials is significant, and they have been successfully applied to various peroxidase-like studies involving catalytic oxidation of the substrate 3,3′,5,5′-tetramethylbenzidine (TMB). However, the limited chemical stability of MOFs in aqueous environments hampers their catalytic applications. To address this inherent drawback and enhance the peroxidase-like activity of MOFs, a method involving adenosine triphosphate (ATP) bonding was proposed. In this study, collaborative materials comprising cobalt MOFs (Co-MOFs) and ATP were utilized as model catalysts for TMB catalysis. The presence of ATP significantly improved the catalytic capability of Co-MOFs over a pH range from 3 to 9 and temperatures ranging from 25 to 60 °C. Notably, at pH 7 and 60 °C, the catalytic efficiency increased by approximately 100 times and an impressive enhancement rate of up to 4600% was achieved respectively. This peroxidase-like catalytic system offers a colorimetric detection assay that selectively detects L-cysteine with a limit of detection as low as 76.2 nM. Incorporating ATP into Co-MOFs presents a novel approach for utilizing MOFs in catalysis that is convenient, straightforward, and gentle.

金属有机框架（MOFs）在类酶材料领域发挥着重要作用，并已成功应用于各种过氧化物酶类研究，包括底物 3,3′,5,5′-四甲基联苯胺（TMB）的催化氧化。然而，MOFs 在水环境中有限的化学稳定性阻碍了它们的催化应用。为了解决这一固有缺陷并增强 MOFs 的过氧化物酶样活性，有人提出了一种涉及三磷酸腺苷（ATP）键合的方法。在这项研究中，由钴 MOFs（Co-MOFs）和 ATP 组成的合作材料被用作 TMB 催化的模型催化剂。在 pH 值为 3 至 9、温度为 25 至 60 ℃ 的条件下，ATP 的存在大大提高了 Co-MOFs 的催化能力。值得注意的是，在 pH 值为 7 和温度为 60 ℃ 的条件下，催化效率分别提高了约 100 倍和 4600% 。这种类似过氧化物酶的催化系统提供了一种比色检测方法，可选择性地检测 L-半胱氨酸，检测限低至 76.2 nM。将 ATP 加入 Co-MOFs 为利用 MOFs 进行催化提供了一种方便、直接和温和的新方法。

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引用次数: 0

Three metal–organic compounds based on [SiMo12O40]4-: Synthesis, structures and properties 基于 [SiMo12O40]4- 的三种金属有机化合物：合成、结构和性质

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2024-09-21 DOI: 10.1016/j.ica.2024.122386

Three polyoxometalate-based metal–organic complexes with the ability to treat pollutants in water were obtained under hydrothermal conditions using two flexible bis(triazole) organic ligands, [Cu(bte)₂(H₂O)]₂[SiMo₁₂O₄₀]·2H₂O (1), [Cu(btb)₂]₂[SiMo₁₂O₄₀]·H₂O (2) and [Cu(btb)₂(H₂O)]₂[SiMo₁₂O₄₀] (3) (bte = 1,2-bis(1,2,4-triazol-1-yl)ethane; btb = 1,4-bis(1,2,4-triazol-1-yl)butane). In compound 1, Cu²⁺ ions are linked by bte into a two-dimensional network layer with [SiMo₁₂O₄₀]^4- anions filled between the layers as guest molecules. In compound 2, [SiMo₁₂O₄₀]^4- anions act as four-connected ligands to coordinate with Cu²⁺ and fill in the pores of the three-dimensional framework constructed by Cu²⁺ and btb. In compound 3, [SiMo₁₂O₄₀]^4- anions act as guest molecules to fill the channels of the two-dimensional layer formed by Cu²⁺ and btb. The electrochemical characteristics were studied, such as cyclic voltammetry, electrocatalytic reduction and oxidation of water contaminants, and current sensing of BrO^3-. The photocatalytic degradation of organic dye pollutant MB (methylene blue) performance was also investigated under visible light conditions.

利用两种灵活的双（三唑）有机配体，在水热条件下获得了三种具有处理水中污染物能力的聚氧化金属基金属有机配合物、[Cu(bte)2(H2O)]2[SiMo12O40]-2H2O（1）、[Cu(btb)2]2[SiMo12O40]-H2O（2）和[Cu(btb)2(H2O)]2[SiMo12O40]（3）（bte = 1,2-双(1,2,4-三唑-1-基)乙烷；btb = 1,4-双（1,2,4-三唑-1-基）丁烷）。在化合物 1 中，Cu2+ 离子通过 bte 连接成二维网络层，[SiMo12O40]4- 阴离子作为客体分子填充在网络层之间。在化合物 2 中，[SiMo12O40]4- 阴离子作为四连接配体与 Cu2+ 配位，并填充在由 Cu2+ 和 btb 构建的三维框架的孔隙中。在化合物 3 中，[SiMo12O40]4- 阴离子作为客体分子填充了 Cu2+ 和 btb 形成的二维层的通道。对其电化学特性进行了研究，如循环伏安法、水污染物的电催化还原和氧化以及 BrO3- 的电流感应。此外，还研究了在可见光条件下光催化降解有机染料污染物 MB（亚甲基蓝）的性能。

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引用次数: 0

Imidobis(tetraphenylphosphinato)lanthanoid(III) complexes: Synthesis by oxidative protolysis, and redox transmetallation/protolysis, structural studies and Hirshfeld surface analysis 亚胺双(四苯基膦)镧系(III)配合物：通过氧化原溶解和氧化还原转金属化/原溶解合成、结构研究和 Hirshfeld 表面分析

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2024-09-20 DOI: 10.1016/j.ica.2024.122385

Redox protolysis of [YbCp₂(dme)] (dme = 1,2-dimethoxyethane) by imidotetraphenyldiphosphinate, ({Ph₂PO}₂NH) LH yields [YbCp{(Ph₂PO)₂N}₂}(MeCN)] 1 and [Yb{(Ph₂PO)₂N}₃] 2 with the last also obtained by oxidative protolysis of Yb(C₆F₅)₂. The complexes [Ln{(Ph₂PO)₂N}₃] ((Ln = Yb 2, Er 3, Gd 4), [Sm{(Ph₂PO)₂N}₃(MeCN)₃] 5 and [Nd{(Ph₂ PO)₂N}₃] 6 have all been prepared by redox transmetallation/protolysis reactions between Yb, Er, Gd, Sm or Nd metals, bispentafluorophenylmercury and proligand LH. Complex 1 is formally eight coordinate with an acetonitrile, cyclopentadienyl (Cp) and two chelating O,O′-(Ph₂PO)₂N ligands, with the MeCN trans to the Cp ring. Complexes 2 and 4·C₇H₈ are six coordinate monomers with three chelating O,O′ diphosphinate ligands. By contrast 5 is a highly symmetrical nine-coordinate monomer with three acetonitrile and three chelating O,O′-L ligands. The three-dimensional Hirshfeld surface (3D-HS) analysis and the two-dimensional fingerprint plots (2D-FP) were quantified for different intermolecular interactions in complexes 2 and 4.

亚胺四苯基二膦酸盐（{Ph2PO}2NH）LH 对 [YbCp2(dme)] （dme = 1,2-二甲氧基乙烷）的氧化还原原解产生 [YbCp{(Ph2PO)2N}2}(MeCN)] 1 和 [Yb{(Ph2PO)2N}3] 2，最后一种也是通过 Yb(C6F5)2 的氧化原解得到的。[Ln{(Ph2PO)2N}3]（Ln = Yb 2、Er 3、Gd 4）、[Sm{(Ph2PO)2N}3(MeCN)3]5 和[Nd{(Ph2 PO)2N}3] 6 复合物都是通过 Yb、Er、Gd、Sm 或 Nd 金属、双五氟苯基汞和原配体 LH 之间的氧化还原/原分解反应制备的。络合物 1 由乙腈、环戊二烯（Cp）和两个螯合 O，O′-（Ph2PO）2N 配体组成，MeCN 反式连接到 Cp 环上。配合物 2 和 4-C7H8 是六坐标单体，带有三个螯合 O,O′二膦酸配体。相比之下，5 是高度对称的九配位单体，具有三个乙腈配体和三个 O,O′-L螯合配体。对配合物 2 和 4 中不同的分子间相互作用进行了三维 Hirshfeld 表面（3D-HS）分析和二维指纹图谱（2D-FP）量化。

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引用次数: 0

Facile CH aryl and OH bonds activation at dirhenium site of [Re2(CO)8(THF)2] complex 在[Re2(CO)8(THF)2]络合物的钌位点轻松激活 CH 芳基键和 OH 键

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2024-09-19 DOI: 10.1016/j.ica.2024.122384

The activation of small molecules is a topic of great interest and previously we reported on the easy activation of different types of EH bonds at the dinuclear complex [Re₂(CO)₈(THF)₂] (1) where labile THF molecules coordinate to adjacent rhenium(0) atoms. Here we extend the reactivity of 1 reporting on the oxidative addition of benzene and toluene at room temperature to give [Re₂(μ-H)(μ-κC-Ar)(CO)₈], Ar = −C₆H₅ (2) and −C₆H₄Me (3). Compound 3 is a new example of μ-κC-Ar dinuclear rhenium complex and has been obtained as para and meta isomers (3a,b). It is known from the literature that 2 can activate arenes and heteroarenes via reductive elimination of benzene and oxidative addition of CH bonds to the dinuclear fragment. Here we have studied the reaction of 2 with C₆D₆ and H₂CC(H)Ph and determined the kinetic constants by ¹H NMR (1.4 × 10⁻⁵ s⁻¹ at 308 K and 1.1 × 10⁻⁵ s⁻¹ at 298 K, respectively). The results indicate that the rate-determining step of the reaction is the reductive elimination of benzene, while the oxidative addition is fast. Water and methanol react with 1 in toluene at room temperature to give the hydroxo and methoxo hydrido complexes [Re₂(μ-H)(μ-OR)(CO)₈], RH (5) and CH₃ (6). On reacting 1 with water in deuterated toluene, and monitoring by ¹H/²H NMR, a preferential deuteration of the hydride site to give [Re₂(μ-D)(μ-OH)(CO)₈] is evidenced. This finding excludes the oxidative addition of water on the dinuclear “Re₂(CO)₈” fragment while supporting a heterolytic addition of water via protonation at the µ-κC-tolyl group, elimination of toluene and addition of OH⁻. Single crystal X-ray diffraction analyses have been performed for complexes 3a, 5 and 6 and their solid state structures have been determined. In particular, the crystal structure of 5 results in a new polymorphic form (5b) and it is discussed in comparison with the already known one (5a).

小分子的活化是一个备受关注的话题，之前我们曾报道过双核复合物 [Re2(CO)8(THF)2] (1) 易于活化不同类型的 EH 键，其中易变的 THF 分子与相邻的铼（0）原子配位。在此，我们扩展了 1 的反应性，报告了苯和甲苯在室温下的氧化加成反应，得到了 [Re2(μ-H)(μ-κC-Ar)(CO)8]，Ar = -C6H5 (2) 和 -C6H4Me (3)。化合物 3 是 μ-κC-Ar 双核铼络合物的一个新例子，以对位和元异构体形式出现（3a,b）。从文献中得知，2 可以通过苯的还原消除和双核片段 CH 键的氧化加成来活化炔和杂环烯。在此，我们研究了 2 与 C6D6 和 H2CC(H)Ph 的反应，并通过 1H NMR 测定了动力学常数（308 K 时分别为 1.4 × 10-5 s-1 和 298 K 时分别为 1.1 × 10-5 s-1）。结果表明，决定反应速率的步骤是苯的还原消除，而氧化加成的速度很快。水和甲醇在室温下与 1 在甲苯中反应，生成氢氧基和甲氧基氢化物[Re2(μ-H)(μ-OR)(CO)8]、RH (5) 和 CH3 (6)。将 1 与水在氚代甲苯中反应，并通过 1H/2H NMR 进行监测，结果表明氢化物位点优先发生氚化反应，生成 [Re2(μ-D)(μ-OH)(CO)8]。这一发现排除了水在双核 "Re2(CO)8 "片段上的氧化加成，同时支持水通过µ-κC-甲苯基团的质子化、甲苯的消除和 OH- 的加成进行异溶解加成。对复合物 3a、5 和 6 进行了单晶 X 射线衍射分析，并确定了它们的固态结构。特别是 5 的晶体结构产生了一种新的多晶型（5b），并与已知的多晶型（5a）进行了比较讨论。

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