European Journal of Inorganic Chemistry最新文献

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Alkali Metal Ion Tuning of a Crown Ether‐Appended Porphyrin for Electrocatalytic CO2 Reduction 碱金属离子调节冠醚添加型卟啉的电催化二氧化碳还原作用

IF 2.524 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

European Journal of Inorganic Chemistry

Pub Date : 2024-08-26 DOI: 10.1002/ejic.202400259

Adarsh Koovakattil Surendran, Elija Veenman, Jana Roithová

Iron‐porphyrin systems are among the best catalysts to reduce selectively CO2 to CO. Electronic modification of the porphyrin skeleton by substituents can enhance the catalytic efficiency of the complexes. In this work, we modified the iron porphyrin complex with crown‐ether auxiliaries and tested the effect of complexation with alkali metals on their electrocatalytic properties for CO2 reduction. The presence of Na+ or K+ resulted in a positive shift of the onset potential by 210 mV while not compromising the catalytic current. This effect was maintained after the immobilization at the vulcanized carbon support, and the catalyst showed the Faradaic efficiency above 90% for CO2 to CO reduction in aqueous solution of NaHCO3 or KHCO3 in a wide range of overpotentials. Hence, host‐guest chemistry at the periphery of the CO2 reduction catalysts can tune the electronic properties of the catalysts and thereby increase the catalytic efficiency.

铁-卟啉系统是将 CO2 选择性还原为 CO 的最佳催化剂之一。通过取代基对卟啉骨架进行电子修饰可以提高络合物的催化效率。在这项工作中，我们用冠醚助剂修饰了铁卟啉配合物，并测试了与碱金属络合对其还原 CO2 的电催化性能的影响。Na+ 或 K+ 的存在导致起始电位正移 210 mV，同时不会影响催化电流。在硫化碳载体上固定后，这种效果得以保持，催化剂在 NaHCO3 或 KHCO3 水溶液中将 CO2 还原为 CO 时，在很宽的过电位范围内，法拉第效率都超过了 90%。因此，二氧化碳还原催化剂外围的主客体化学反应可以调节催化剂的电子特性，从而提高催化效率。

引用次数: 0

Vanadium(V/IV) Oxido Complexes: Potential as Bases in Frustrated Lewis Pairs 钒（V/IV）氧化络合物：作为受挫路易斯配对碱的潜力

IF 2.524 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

European Journal of Inorganic Chemistry

Pub Date : 2024-08-23 DOI: 10.1002/ejic.202400473

Angela Milinkovic, Antoine Dupé, Nadia C. Mösch-Zanetti

Frustrated Lewis Pairs (FLP) have found exciting access in catalysis and small molecule activation. Here, we describe the potential of two vanadium(V) oxido complexes with monoanionic bidentate N,O donors, [VOCl(LCF3)2] (1a), [VOCl(LH)2] (1b) as bases in FLPs. Upon reaction of 1a with the Lewis acid B(C6F5)3 the FLP [VOCl(LCF3)2]/B(C6F5)3 (1a/B(C6F5)3) was observed. Addition of Ph3SiH led to the reduction of VV to VIV under formation of the adduct [V{OB(C6F5)3}(LCF3)2] (2a) while FLP reactivity was not observed. Dissolving 2a in CH3CN leads to the VIV oxido complex, [VO(LCF3)2] (3a). In contrast, when 1b was reacted with B(C6F5)3, a VIV oxido complex [VO(LH)2] (3b) was obtained. Upon addition of B(C6F5)3 to 3b no reaction leading to the expected adduct such as 2a could be observed. Only few crystals deriving from a disproportion reaction could be identified as an adduct dimer [V{OB(C6F5)3}LH(μ‐O)]2. While FLP reactivity could not be found yet with the described systems, the redox labile nature and versatility of the metal complexes are demonstrated.

受挫路易斯对（FLP）在催化和小分子活化方面的应用令人兴奋。在这里，我们描述了两种具有单阴离子双齿 N、O 给体的钒(V)氧化络合物[VOCl(LCF3)2] (1a)和[VOCl(LH)2] (1b) 作为受阻路易斯对碱基的潜力。当 1a 与路易斯酸 B(C6F5)3 反应时，观察到 FLP [VOCl(LCF3)2]/B(C6F5)3 (1a/B(C6F5)3)。加入 Ph3SiH 后，在形成加合物 [V{OB(C6F5)3}(LCF3)2] (2a) 的情况下，VV 还原成 VIV，但未观察到 FLP 反应。将 2a 溶于 CH3CN 会生成 VIV 氧代配合物[VO(LCF3)2]（3a）。相反，当 1b 与 B(C6F5)3 反应时，得到了 VIV 氧化络合物 [VO(LH)2] (3b)。在 3b 中加入 B(C6F5)3 后，无法观察到导致预期加合物（如 2a）的反应。只有少数来自歧化反应的晶体可以被鉴定为加合物二聚体 [V{OB(C6F5)3}LH(μ-O)]2。虽然所述体系尚未发现 FLP 反应性，但金属配合物的氧化还原易变性和多功能性已得到证实。

引用次数: 0

Front Cover: C−H Bond Activation Facilitated by Nickel(II) Complexes Having Mighty Claws (Eur. J. Inorg. Chem. 24/2024) 封面：具有强大爪子的镍(II)配合物促进的 C-H 键活化（Eur.）

IF 2.2 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

European Journal of Inorganic Chemistry

Pub Date : 2024-08-23 DOI: 10.1002/ejic.202482401

Anjana Rajeev, Arnold Tharun Thomas, Athulya Das, Muniyandi Sankaralingam

The Front Cover demonstrates the oxidation of cyclohexane to cyclohexanol catalysed by nickel(II) complexes of aminoquinoline-based pincer ligands with m-CPBA as the oxidant. The crab represents the general structure of ligands, and its claws hold the nickel atom to indicate the coordination mode. A stream of bubbles from the bottom of the circle depicts the supply of m-CPBA oxidant during the reaction. More information can be found in the Research Article by M. Sankaralingam and co-workers.

封面展示了以 m-CPBA 为氧化剂的氨基喹啉基钳形配体的镍(II)配合物催化环己烷氧化成环己醇的过程。螃蟹代表配体的一般结构，它的爪子抓着镍原子，表示配位模式。圆圈底部的气泡流描绘了反应过程中 m-CPBA 氧化剂的供应情况。更多信息，请参阅 M. Sankaralingam 及其合作者的研究文章。

引用次数: 0

Single‐Electron Oxidation, Chloride Abstraction, and Hydride‐Induced Decomposition of a Dichloro‐Bis(Germylene) 二氯双（亚甲基）的单电子氧化、氯化物萃取和氢化物诱导分解

IF 2.524 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

European Journal of Inorganic Chemistry

Pub Date : 2024-08-23 DOI: 10.1002/ejic.202400422

Jingjing Cui, Yiyi He, Cauê P. Souza, Jonas Weiser, Maximilian Dietz, Ivo Krummenacher, Rian D. Dewhurst, Holger Braunschweig, Felipe Fantuzzi

In this work we explore the reactivity of a dichloro‐bis(germylene) compound that features a naphthyridine diimine (NDI) ligand, denoted NDI‐Ge 2Cl2. Upon reaction with the oxidant [Cp2Fe][BArF4] (Cp = C5H5, BArF4 = [{3,5‐(CF3)2C6H3}4B]), we observed the formation of the radical species [NDI‐Ge2Cl2]•+[BArF4]−. Furthermore, the introduction of Na[BArF4] induced a single chloride anion abstraction process, resulting in the formation of [NDI‐Ge2Cl][BArF4]. The addition of Li[HB(sBu)3] to NDI‐Ge2Cl2 led to the generation of NDI‐Ge, presumably via a Cl/H exchange pathway followed by a decomposition process.

在这项研究中，我们探索了一种二氯双（亚甲基）化合物的反应性，该化合物具有萘啶二亚胺（NDI）配体，命名为 NDI-Ge 2Cl2。与氧化剂 [Cp2Fe][BArF4]（Cp = C5H5，BArF4 = [{3,5-(CF3)2C6H3}4B]）反应后，我们观察到形成了自由基物种 [NDI-Ge2Cl2]-+[BArF4]-。此外，Na[BArF4]的引入诱导了单个氯阴离子的抽取过程，从而形成了[NDI-Ge2Cl][BArF4]。在 NDI-Ge2Cl2 中加入 Li[HB(sBu)3] 会生成 NDI-Ge，这可能是通过 Cl/H 交换途径，然后再进行分解过程。

引用次数: 0

Synthesis and Theoretical Evaluation of New Copper(II) Complexes Associated with a Crystalline Schiff Base: DNA/BSA Protein Interaction, Radical Scavenging and Cytotoxicity 与结晶希夫碱有关的新铜（II）配合物的合成与理论评估：DNA/BSA 蛋白相互作用、自由基清除和细胞毒性

IF 2.524 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

European Journal of Inorganic Chemistry

Pub Date : 2024-08-22 DOI: 10.1002/ejic.202400302

Himanshi Sharma, Madhvesh pathak

A crystalline dihydroxy substituted Schiff base ligand [LH] was involved in the synthesis of three copper(II) complexes viz [Cu(LH)2] (Cu1), [Cu(LH)(bpy)] (Cu2) and [Cu(LH)(phen)] (Cu3) (bpy= 2,2’‐bipyridine and phen= 1,10‐phenanthroline). FTIR, ESI‐MS, elemental analysis, ESR studies and NMR techniques were employed to characterize all the newly synthesized compounds. The molecular structure of ligand and complexes were optimized using density functional theory (DFT) at B3LYP/LanL2DZ levels in the gas phase. According to DFT investigations Cu1 exhibits tetragonally distorted octahedral geometry around Cu(II) while Cu2 and Cu3 appeared in penta‐coordination as distorted trigonal bipyramidal geometry. UV‐Vis, fluorescence and viscosity titrations were used to examine the metal complex interactions with CT‐DNA and BSA protein. The binding results suggest that the complexes bind to DNA via groove binding mode. Molecular docking was performed to analyse the binding interaction of complexes with BSA and DNA. Antioxidant investigation indicates that the Cu1 possesses remarkable ability to scavenge radicals against DPPH due to the lowest IC50 value 211.20 mg/mL. In‐vitro cytotoxicity was assessed against MCF‐7 breast cancer cells where Cu1 was found to have superiority in cytotoxicity with IC50 value 52.35 mm over other analogues.

在合成三种铜(II)配合物时使用了一种二羟基取代的希夫碱配体[LH]晶体，即[Cu(LH)2]（Cu1）、[Cu(LH)(bpy)]（Cu2）和[Cu(LH)(phen)]（Cu3）（bpy= 2,2'-联吡啶，phen= 1,10-菲罗啉）。傅立叶变换红外光谱、ESI-MS、元素分析、ESR 研究和 NMR 技术用于表征所有新合成的化合物。在气相条件下，利用密度泛函理论（DFT）在 B3LYP/LanL2DZ 水平上对配体和配合物的分子结构进行了优化。根据 DFT 研究，Cu1 围绕 Cu(II)呈现出四方扭曲八面体几何结构，而 Cu2 和 Cu3 则呈现出五配位的扭曲三叉双锥几何结构。利用紫外可见光、荧光和粘度滴定法研究了金属复合物与 CT-DNA 和 BSA 蛋白的相互作用。结合结果表明，复合物通过沟结合模式与 DNA 结合。分子对接分析了复合物与 BSA 和 DNA 的结合相互作用。抗氧化研究表明，由于 Cu1 的最低 IC50 值为 211.20 毫克/毫升，因此具有显著的清除 DPPH 自由基的能力。在对 MCF-7 乳腺癌细胞进行体外细胞毒性评估时，发现 Cu1 的细胞毒性优于其他类似物，IC50 值为 52.35 mm。

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引用次数: 0

Ultrafast Structural Dynamics of a Photoexcited Mn‐Fe Charge‐Transfer Material in the Polaronic and Phase Transition regimes 光激发锰铁电荷转移材料在极性和相变状态下的超快结构动力学研究

IF 2.524 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

European Journal of Inorganic Chemistry

Pub Date : 2024-08-22 DOI: 10.1002/ejic.202400371

Marius Hervé, Gael Privault, Elzbieta Trzop, Shintaro Akagi, Yves Watier, Serhane Zerdane, Ievgenia Chaban, Ricardo Guillermo Torres Ramirez, Céline Mariette, Alix Volte, Marco Cammarata, Hiroko Tokoro, Matteo Levantino, Eric Collet, Shin-ichi Ohkoshi

The Rb0.94Mn0.94Co0.06[Fe(CN)6]0.98 material was designed to exhibit a 75 K wide thermal hysteresis around room temperature, associated with a bistability between the low temperature MnIIIFeII tetragonal phase and the high temperature MnIIFeIII cubic phase. We have recently shown that a single laser pulse can be used to drive, at room temperature, the photoinduced phase transition from the MnIIIFeII tetragonal phase to the MnIIFeIII cubic phase. By using a specific powder sample streaming technique, we could monitor by time‐resolved X‐ray diffraction how the ultrafast out‐of‐equilibrium dynamics, imposed by the structural relaxation around the local photoinduced charge transfer, changes with the fluence of the laser pulse. In this paper we present a detailed structural analysis of the crystalline reorganizations associated with the charge‐transfer in different regimes of photoexcitation. In the low excitation polaronic regime, the photoinduced charge transfer is local and accompanied by anisotropic distortion of the Mn coordination sphere and of the tetragonal lattice. In the high excitation regime, a macroscopic and cooperative charge‐transfer phase transition occurs towards the cubic lattice, where the coordination around the Mn reaches octahedral symmetry.

Rb0.94Mn0.94Co0.06[Fe(CN)6]0.98材料被设计成在室温附近表现出75 K宽的热滞后，这与低温MnIIIFeII四方相和高温MnIIFeIII立方相之间的双稳态性有关。我们最近的研究表明，在室温下，单个激光脉冲可用于驱动从 MnIIIFeII 四方相到 MnIIFeIII 立方相的光诱导相变。通过使用特定的粉末样品流技术，我们可以用时间分辨 X 射线衍射法监测局部光诱导电荷转移周围的结构弛豫所引起的超快失衡动力学如何随激光脉冲的通量而变化。在本文中，我们对不同光激发状态下与电荷转移相关的晶体重组进行了详细的结构分析。在低激发极性条件下，光诱导的电荷转移是局部的，并伴随着锰配位层和四方晶格的各向异性畸变。在高激发机制下，向立方晶格发生了宏观和合作的电荷转移相变，锰周围的配位达到了八面体对称。

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引用次数: 0

Chiral Effect on the Spin Crossover Behavior in a Pair of Co(II) Enantiomers and their Racemic Complex 一对 Co（II）对映体及其外消旋复合物的手性效应对自旋交叉行为的影响

IF 2.2 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

European Journal of Inorganic Chemistry

Pub Date : 2024-08-21 DOI: 10.1002/ejic.202400201

Xin-Yang Zhang, Hui-Ying Sun, Du-Yong Chen, Xin-Feng Li, Jing-Yi Xiao, Yin-Shan Meng, Tao Liu

The combination of spin crossover (SCO) with chirality has caught increasing research interest owing to its potential applications in the fields of multifunctional magnetic molecular materials and devices. In this work, we synthesized a pair of homochiral Co(II) SCO complexes and their racemic complex by applying chiral Schiff base terimine ligands modified by naphthyl group. Single-crystal X-ray diffraction results showed that the chiral ligands retained chirality after coordination with Co(II) ion, giving rise to a pair of enantiomeric Co(II) complexes in the RR and SS configurations, respectively. The circular dichroism spectroscopy demonstrated the enantiomeric nature of the homochiral complexes. The enantiomers exhibited similar thermally induced SCO, while the racemate was trapped in the high spin state. The differences in SCO behavior between the homochiral and racemic complexes are attributed to different supramolecular interactions. This work provides a feasible approach to constructing new chiral SCO materials and offers perspectives in developing switchable nonlinear optical magnetic materials.

自旋交叉（SCO）与手性的结合因其在多功能磁性分子材料和器件领域的潜在应用而引起了越来越多的研究兴趣。在这项工作中，我们利用萘基修饰的手性希夫碱萜胺配体合成了一对同手性 Co(II) SCO 复合物及其外消旋复合物。单晶 X 射线衍射结果表明，手性配体与 Co(II) 离子配位后保留了手性，从而产生了一对分别为 RR 和 SS 构型的对映体 Co(II) 复合物。圆二色光谱证明了同手性配合物的对映体性质。对映体表现出相似的热诱导 SCO，而外消旋体则处于高自旋状态。同手性复合物和外消旋复合物在 SCO 行为上的差异归因于不同的超分子相互作用。这项工作为构建新型手性 SCO 材料提供了可行的方法，并为开发可切换的非线性光学磁性材料提供了前景。

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引用次数: 0

Thermally Stable Heteroleptic trans-Bis(chelate) Ruthenium(II) Complex Bearing 2,2'-Bipyridine and Acetylacetonato: Synthesis, Isomerization, and Crystal Structure 含有 2,2'-联吡啶和乙酰丙酮的热稳定异极反式双（螯合物）钌（II）络合物：合成、异构化和晶体结构

IF 2.524 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

European Journal of Inorganic Chemistry

Pub Date : 2024-08-19 DOI: 10.1002/ejic.202400243

Mari TOYAMA, Daichi Fujimoto, Yusuke Kawakami, Shiho Tanaka

Thermally stable trans-bis(chelate)-type Ru(II) complexes are challenging to prepare owing to steric hindrance between the two chelate ligands. Herein, we investigated the isomerization of a heteroleptic cis-bis(chelate) complex to obtain its trans form. cis-[Ru(acac)(bpy)(dmso-S)2](OTf)·0.5H2O (1·(OTf)·0.5H2O; acac− = acetylacetonato; bpy = 2,2’-bipyridine; dmso = dimethyl sulfoxide; OTf– = CF3SO3–) was prepared by reacting trans(O,S)-[Ru(bpy)(dmso-S)2(dmso-O)2](OTf)2 (P0) with Li(acac) in acetone at 298 K. In 1·(OTf)·0.5H2O, the two labile dmso-O ligands of P0 were replaced by an acac– ligand. The dihedral angle between the chelate rings of bpy and acac– in 1+ was 76.7°, suggesting steric hindrance between ligands owing to the two bulky dmso-S ligands at the cis position. 1·(OTf)·0.5H2O was thermally stable in DMSO and acetone; however, in methanol and water, a dmso-S ligand was dissociated from 1+, and the complex isomerized to trans-[Ru(acac)(bpy)(dmso-S)(solvent)]+. Refluxing of 1·(OTf)·0.5H2O in methanol for 18 h, evaporation to dryness under vacuum, and treatment with water yielded trans-[Ru(acac)(bpy)(dmso-S)(OH2)](OTf) (2·(OTf)) with excellent purity. 2·(OTf) was characterized by X-ray crystallography, elemental analysis, and 1H NMR spectroscopy. As expected, steric hindrance was not observed between the trans-arranged bpy and acac−, and the two chelates laid flat on the equatorial plane in 2+.

由于两个螯合配体之间存在立体阻碍，制备热稳定的反式双（螯合物）型 Ru（II）配合物具有挑战性。在此，我们研究了异极顺式双（螯合物）配合物的异构化，以获得其反式形式。顺式-[Ru(acac)(py)(dmso-S)2](OTf)-0.5H2O（1-(OTf)-0.5H2O；acac- = 乙酰丙酮；bpy = 2,2'-联吡啶；dmso = 二甲亚砜；OTf- = CF3SO3-）是通过反式（O，S）-[Ru(bpy)(dmso-S)2(dmso-O)2](OTf)2 (P0)与 Li(acac)在丙酮中于 298 K 下反应制备的。在 1-(OTf)-0.5H2O 中，P0 的两个易溶的 dmso-O 配体被一个 acac 配体取代。1+ 中 bpy 和 acac- 的螯合环之间的二面角为 76.7°，这表明由于顺式位置上有两个笨重的 dmso-S 配体，配体之间存在立体阻碍。在二甲基亚砜和丙酮中，1-(OTf)-0.5H2O 具有热稳定性；但在甲醇和水中，dmso-S 配体从 1+ 中解离，复合物异构为反式-[Ru(acac)(py)(dmso-S)(溶剂)]+。将 1-(OTf)-0.5H2O 在甲醇中回流 18 小时，真空蒸发至干，然后用水处理，就得到了反式-[Ru(acac)(py)(dmso-S)(OH2)](OTf) （2-(OTf)），纯度极高。2-(OTf) 通过 X 射线晶体学、元素分析和 1H NMR 光谱进行了表征。不出所料，反式排列的 bpy 和 acac- 之间没有发现立体阻碍，两种螯合物平铺在 2+ 的赤道平面上。

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引用次数: 0

Interplay of Metal Ions and Posttranslational Modifications in Proteins 金属离子与蛋白质翻译后修饰的相互作用

IF 2.524 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

European Journal of Inorganic Chemistry

Pub Date : 2024-08-19 DOI: 10.1002/ejic.202400175

Massimiliano Peana, Tomasz Frączyk, Maria Antonietta Zoroddu

Posttranslational modifications (PTMs) and metal ions are integral players in the complex regulatory orchestra governing protein function. Several metal ions, including zinc, iron, copper, and others, intricately influence protein structure and activity as cofactors. Concurrently, PTMs, such as phosphorylation, acetylation, and ubiquitination, add an additional layer of complexity to the proteome, dynamically shaping cellular responses. Understanding this bidirectional relationship is crucial for unraveling the complex web of cellular regulation. This review explores the reciprocal impact of metal ions on PTMs and vice versa and provides examples and insights into how metal ions modulate PTMs and, conversely, how PTMs influence metal‐binding proteins, shedding light on the complex crosstalk between these two crucial facets of cellular biology. This interplay is not only central to cellular homeostasis but also holds implications for diseases associated with dysregulated metal‐ion and PTM processes.

翻译后修饰（PTM）和金属离子是调节蛋白质功能的复杂乐队中不可或缺的角色。锌、铁、铜等几种金属离子作为辅助因子，对蛋白质的结构和活性产生着错综复杂的影响。同时，磷酸化、乙酰化和泛素化等 PTM 为蛋白质组增加了一层复杂性，动态地影响着细胞反应。了解这种双向关系对于揭示复杂的细胞调控网络至关重要。这篇综述探讨了金属离子对 PTMs 的相互影响，反之亦然，并提供了金属离子如何调节 PTMs 以及 PTMs 如何影响金属结合蛋白的实例和见解，揭示了细胞生物学这两个重要方面之间复杂的相互影响。这种相互作用不仅是细胞平衡的核心，而且对与金属离子和 PTM 过程失调相关的疾病也有影响。

引用次数: 0

Reactivity of the p‐Cymene‐Ru Complex with Two Phenylamines for Metathesis Polymerization of Norbornene Compared to the Reactivity of Complexes with a Single Benzylamine or Dibenzylamine 对伞花烃-Ru 与两个苯胺配合物在降冰片烯 Metathesis 聚合反应中的反应活性与与单个苄胺或二苄胺配合物的反应活性的比较

IF 2.524 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

European Journal of Inorganic Chemistry

Pub Date : 2024-08-17 DOI: 10.1002/ejic.202400319

Eliada A Silva, Pedro H. O. Santiago, Javier A Ellena, Antônio G. S. Oliveira-Filho, Ana Paula Lima Batista, Benedito S Lima-Neto

The complexes [RuCl(Cy)(NH2Ph)2]Cl (1), [RuCl2(Cy)(NH2Bz)] (2), and [RuCl2(Cy)(NHBz2)] (3) were obtained under the same conditions from [RuCl2(Cy)]2; Cy = η6‐p‐cymene, Ph = phenyl, and Bz = benzyl. X‐ray crystallography showed the additional NH2Ph ligand in 1, differing from the neutral mono‐amine complexes 2 and 3. The number of amines in the complexes does not show clear correlations with s‐donor character or steric hindrance of the amines. Different reactivities were observed for ROMP of norbornene (NBE), measured from batch reactions and by kinetic studies using Raman and 1H NMR spectroscopy, with semiquantitative conversions: with 1 up to 30 °C and around 40% with 2 and 3. DFT calculations confirmed the proposal that the reactions occur with the release of an amine in complex 1 through a dissociative mechanism, while complexes 2 and 3 react through an associative mechanism with loss of amines. The presence of the amine in the propagation species of 1 indicates the participation of the amine as an auxiliary ligand. All carbene species are of the η2‐p‐cymene type, and the catalytic cycle occurs with a 14‐16‐14 electron counting mechanism.

在相同条件下，从[RuCl2(Cy)]2 得到了[RuCl2(Cy)(NH2Ph)2]Cl（1）、[RuCl2(Cy)(NH2Bz)]（2）和[RuCl2(Cy)(NHBz2)]（3）复合物；Cy = η6-对伞花烃，Ph = 苯基，Bz = 苄基。X 射线晶体学显示，1 中含有额外的 NH2Ph 配体，与中性单胺复合物 2 和 3 不同。复合物中胺的数量与 s-给体性质或胺的立体阻碍没有明显的相关性。通过批量反应以及使用拉曼光谱和 1H NMR 光谱进行动力学研究，观察到降冰片烯 (NBE) 的 ROMP 具有不同的反应活性。DFT 计算证实了以下建议：反应发生时，络合物 1 中的胺通过解离机理释放出来，而络合物 2 和 3 则通过关联机理发生反应，同时胺也会流失。胺在 1 的传播物种中的存在表明胺作为辅助配体参与了反应。所有碳烯种类均为η2-p-氰烯类型，催化循环以 14-16-14 电子计数机制进行。

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