Journal of Organometallic Chemistry最新文献_第9页

The role of ortho-aryl halogen effects in iminopyridyl Ni(II) and Pd(II) catalysts for ethylene (co)oligomerization 邻芳基卤素效应在亚胺吡啶基Ni（II）和Pd（II）催化剂中对乙烯（co）齐聚反应的作用

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-10-22 DOI: 10.1016/j.jorganchem.2025.123910

Mengyao Zhang , Yan Wang , Shengyu Dai

A series of ortho-aryl-halogenated (F, Cl, Br) iminopyridyl Ni(II) and Pd(II) complexes were synthesized and evaluated in ethylene (co)oligomerization. The nickel catalysts exhibited high activity (up to 7.62 × 10⁶ g/(mol·h)) in ethylene oligomerization, producing low-molecular-weight (337–589 g/mol), highly branched (88–122 branches/1000C) oligomers. Larger halogen substituents enhanced activity, increased molecular weight, and reduced branching density, suggesting suppressed chain transfer via steric and electronic modulation. The palladium catalysts showed moderate activity (0.8–7.23 × 10⁴ g/(mol·h)), generating hyperbranched oligomers (124–151 branches/1000C) with temperature-dependent molecular weights (260–684 g/mol). In ethylene–methyl acrylate (MA) co-oligomerization, Pd catalysts achieved high MA incorporation (5–21 mol%) while maintaining low molecular weights (263–344 g/mol) and high branching densities (144–165 branches/1000C). Notably, larger halogens improved co-oligomerization activity but reduced MA insertion, likely due to steric hindrance. These findings highlight the dual role of ortho-aryl halogens in tuning catalytic performance through electronic and steric effects, offering a strategy for designing tailored ethylene oligomer architectures.

合成了一系列邻芳基卤代（F, Cl, Br）亚氨基吡啶基Ni（II）和Pd（II）配合物，并在乙烯（co）齐聚反应中进行了评价。镍催化剂在乙烯低聚反应中表现出较高的活性（高达7.62 × 10 26 g/(mol·h)），产生低分子量（337 ~ 589 g/mol）、高支链（88 ~ 122支/1000C）的低聚物。较大的卤素取代基增强了活性，增加了分子量，降低了分支密度，表明通过位阻和电子调制抑制了链转移。钯催化剂表现出中等活性（0.8-7.23 × 10⁴g/(mol·h)），产生高支化低聚物（124-151支/1000C），分子量（260-684 g/mol）依赖于温度。在乙烯-丙烯酸甲酯（MA）共齐聚反应中，钯催化剂在保持低分子量（263-344 g/mol）和高分支密度（144-165支/1000C）的同时，获得了高MA掺杂率（5-21 mol%）。值得注意的是，较大的卤素提高了共聚活性，但减少了MA插入，可能是由于位阻。这些发现强调了邻芳基卤素在通过电子和空间效应调节催化性能方面的双重作用，为设计量身定制的乙烯低聚物结构提供了策略。

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引用次数: 0

A mononuclear copper(II) complex supported by ferrocene-containing chalcone Schiff-base ligands: synthetic reaction and structural characterization 含二茂铁查尔酮席夫碱配体负载的单核铜（II）配合物：合成、反应和结构表征

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-10-21 DOI: 10.1016/j.jorganchem.2025.123907

Yi-Jie Li, Zhi-Cui Zhang, Tian-Tian Sun, Ai-Quan Jia, Qian-Feng Zhang

Six ferrocene-containing chalcone Schiff-base ligands [Fc-CHCHC(O)(4- C₆H₄)NCH(2-OHAr) (L1H: Ar = C₆H₄; L2H: Ar = 5-Cl-C₆H₃; L3H: Ar = 3,5-Br₂C₆H₂; L4H: Ar = 5-NO₂C₆H₃; L5H: Ar = 3,5-^tBu₂C₆H₂; L6H: Ar = 3-OMe-C₆H₃) and their copper(II) complexes [Cu(L1)₂ (1), Cu(L2)₂ (2), Cu(L3)₂ (3), Cu(L4)₂ (4), Cu(L5)₂ (5) and Cu(L6)₂ (6)] were synthesized. Molecular structures of the ferrocenoyl Schiff-base ligand L1H and mononuclear copper(II) complex 1 were unambiguously confirmed by single-crystal X-ray crystallography along with microanalyses and characterization of their Fourier transform infrared (FT-IR) and Ultraviolet-visible (UV–vis) spectroscopies. Moreover, the mononuclear copper(II) complex 1 was determined by powder X-ray diffraction (PXRD). In addition, six ferrocenoyl Schiff-base ligands were all characterized by ¹H NMR, ¹³C NMR and mass spectroscopies. The stability of their copper(II) complexes at different temperatures were also investigated by thermogravimetric analysis. Electrochemical properties of these ligands and corresponding copper(II) complexes were also investigated.

合成了6种含二茂铁查尔酮希夫碱配体[Fc-CHCHC(O)(4- C6H4)NCH(2- ohar)] （L1H: Ar = C6H4; L2H: Ar = 5- cl - c6h3; L3H: Ar = 3,5- br2c6h2; L4H: Ar = 5- no2c6h3; L5H: Ar = 3,5- tbu2c6h2; L6H: Ar = 3- ome - c6h3）及其铜（II）配合物[Cu(L1)2 (1), Cu(L2)2 (2), Cu(L3)2 (3), Cu(L4)2 (4), Cu(L5)2 (5), Cu(L6)2(6)]。二茂铁基席夫碱配体L1H和单核铜（II）配合物1的分子结构通过单晶x射线晶体学、微观分析以及傅里叶变换红外（FT-IR）和紫外可见（UV-vis）光谱的表征得到了明确的证实。此外，采用粉末x射线衍射（PXRD）对单核铜（II）配合物1进行了测定。此外，六种二茂铁基席夫碱配体均通过1H NMR、13C NMR和质谱进行了表征。用热重分析法考察了它们的铜（II）配合物在不同温度下的稳定性。研究了这些配体和相应的铜（II）配合物的电化学性质。

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引用次数: 0

Transfer hydrogenation of ketones to secondary alcohols catalyzed by new Ruthenium(II) Heterocyclic hydrazone complexes 新型钌（II）杂环腙配合物催化酮类转移加氢制仲醇

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-10-21 DOI: 10.1016/j.jorganchem.2025.123905

Jayapratha Gunasekaran , Pradeep Muthurathinam , Kavinraj Venkatachalam , Narmatha Venkatesan , Rajashri Varadarasu , Luis G. Alves , Ana M. Martins , Shanmuga Bharathi Kuppannan

A new class of half-sandwich ruthenium(II)-p-cymene complexes supported by η⁶-arene and (N, O) heterocyclic thiophene-based Schiff base hydrazone ligands has been synthesized and characterized by FT-IR, UV–Visible spectrophotometry, NMR, ESI-MS spectrometry and single-crystal X-ray diffraction techniques. All the ruthenium(II) complexes were tested as catalysts for the transfer hydrogenation of ketones to secondary alcohols. The reaction conditions were optimized, the complex C³ [Ru(η⁶-p-cymene)(Cl)(L³)](L³ = N’-((1H-indol-2-yl)methylene)thiophene-2-carbohydrazide) showed better catalytic activity than the others. The conditions for the catalytic reactions were optimized with 0.2 mol% of complex, C³ in 5 ml of isopropanol and KOH at room temperature. This catalytic transfer hydrogenation of ketones proceeds through four major steps i.e., β-elimination, nucleophilic attack, hydride insertion and proton transfer. In addition, with this reaction condition our catalyst possesses a wide range of substrate tolerance viz., substrates of aryls with electron withdrawing/ electron donating/bifunctional groups, diaryls and aliphatic ketones. We have also compared the efficiency of our catalytic system against the existed ones and discussed.

合成了一类新型的由η - 6-芳烃和（N， O）杂环噻吩基希夫碱配体负载的半夹心钌(II)-对伞花烃配合物，并用FT-IR、紫外可见分光光度法、核磁共振、ESI-MS谱法和单晶x射线衍射技术对其进行了表征。所有钌（II）配合物都作为酮转移加氢制仲醇的催化剂进行了测试。优化了反应条件，络合物C3 [Ru（η - 6-对伞花烯）（Cl）（L3）]（L3 = N′-（（1h -吲哚-2-基）亚甲基）噻吩-2-碳酰肼）的催化活性较好。在室温条件下，以0.2 mol%的络合物、5 ml异丙醇中的C3和KOH为催化剂，优化了催化反应的条件。酮的催化转移氢化反应经过四个主要步骤，即β消除、亲核攻击、氢化物插入和质子转移。此外，在这种反应条件下，我们的催化剂具有广泛的底物耐受性，即具有吸电子/供电子/双官能团的芳基，二芳基和脂肪酮的底物。并与现有的催化体系进行了效率比较和讨论。

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引用次数: 0

Cycloaddition of CO2 with epoxides into cyclic carbonates catalyzed by cobalt(II or II/III)-arylhydrazonates 钴（II或II/III）-芳酰腙催化CO2与环氧化物环加成成环状碳酸盐

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-10-21 DOI: 10.1016/j.jorganchem.2025.123901

Tahir A. Javadzade , Sevinc R. Hajiyeva , Famil M. Chyragov , Ana V.M. Nunes , Jamal Lasri , Sahil Z. Hamidov , Khudayar I. Hasanov , Kamran T. Mahmudov

A series of known cobalt complexes, [Co(HL¹)₂(H₂O)₄]·2H₂O (1) (HL¹ = 4-(2-(2,4-dioxopentan-3-ylidene)hydrazineyl)benzoate), [Co(μ-HL²)(H₂O)(DMF)]₂·DMF (2) (HL² = (Z)-1-(2-carboxylatophenyl)-2-(1-cyano-2-imino-2-methoxyethylidene)hydrazin-1-ide), [Co^II(H₂O)₂(DMF)₂{Co^III(HL³)₂}₂]·2H₂O (3) (HL³ = (Z)-1-(2-carboxylatophenyl)-2-(1,3-dioxo-1-(phenylamino)butan-2-ylidene)hydrazin-1-ide), [Co^II(μ-HL³)(MeOH)₂]_n (4) and [Co^II(H₂O)₄{Co^III(HL⁴)₂}₂]·12H₂O (5) (HL⁴ = 1-(2-carboxylatophenyl)-2-(4,4-dimethyl-2,6-dioxocyclohexylidene)hydrazin-1-ide), were synthesized and applied as catalysts in the coupling of CO₂ with epoxides in the presence and absence of tetrabutylammonium chloride (TBACl), tetrabutylammonium bromide (TBABr), and tetrabutylammonium iodide (TBAI). Dependent on the nature of the starting epoxide, moderate to good yields (ranging from 31 to 74 %) of the cyclic carbonates were achieved in the reactions catalyzed by 3 under appropriate conditions (24 h, 60 °C and 40 bar pressure).

已知的一系列钴配合物，[Co(HL1)2(H2O)4]·2H2O (1) （HL1 = 4-（2-（2,4-二氧基-3-酰基）肼基）苯甲酸酯），[Co(μ-HL2)(H2O)(DMF)]2·DMF (2) (HL2 = （Z)-1-（2-羧基-2-亚胺-2-甲氧基乙基）肼基），[CoII(H2O)2(DMF)2{CoIII(HL3)2}2]·2H2O (3) (HL3 = (Z)-1-（2-羧基- latophenyl)-2-（1,3-二氧基-1-（苯基氨基）丁基-2-酰基）肼基），合成了[CoII(μ-HL3)(MeOH)2]n(4)和[CoII(H2O)4{CoIII(HL4)2}2]·12H2O (5) (HL4 = 1-（2-羧基苯基）-2-（4,4-二甲基-2,6-二氧环己基）肼-1-ide)，并在四丁基氯化铵（TBACl）、四丁基溴化铵（TBABr）和四丁基碘化铵（TBAI）存在和不存在的情况下作为催化剂用于CO2与环氧化物的偶联反应。根据起始环氧化物的性质，在适当的条件下（24小时，60℃，40 bar压力），由3催化的反应中，环状碳酸盐的收率为中等至良好（31%至74%）。

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引用次数: 0

1,2,3-Triazoles in corrosion protection: Chemistry, ligand properties, coordination bonding and interfacial behavior 1,2,3-三唑在防腐中的应用：化学、配体性质、配位键和界面行为

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-10-20 DOI: 10.1016/j.jorganchem.2025.123900

Chandrabhan Verma , Lipiar K.M.O. Goni , Ibrahim Y. Yaagoob , Renad A. Alyami , Akram Alfantazi , Mohammad A. Jafar Mazumder

1,2,3-Triazoles have emerged as nitrogen-rich heterocycles with multifunctional applications in corrosion protection, owing to their versatile coordination chemistry, chemical stability, tailorable physicochemical properties, unique electron structure, and broad functional utility in materials science. This review article provides a comprehensive overview of synthesis, characterization, coordination chemistry, and corrosion inhibition potential of 1,2,3-triazole derivatives. Various approaches to metal-catalyzed azide-alkyne cycloaddition, as well as metal-free and organocatalyst-based click chemistry for synthesizing 1,2,3-triazole-based systems, have been discussed in detail. A systematic literature survey has been conducted on these heterocyclic compounds, which exhibit strong inhibitory performance against various metals and alloys, including mild steel, copper, and aluminum, in acidic, neutral, and saline environments. The article also describes the ligand properties of triazole derivatives, such as non-innocent behavior, donation, retro-donation, effect of resonance, and coordination modes, that facilitate their interaction with metallic d-orbitals. In general, this work combines the practical advancements and chemical foundations of 1,2,3-triazoles in corrosion science, providing recommendations for the development of next-generation inhibitors that are both environmentally friendly and highly efficient.

1,2,3-三唑具有多种配位化学性质、化学稳定性、可调整的物理化学性质、独特的电子结构以及在材料科学中的广泛功能用途，已成为具有多种防腐功能的富氮杂环化合物。本文综述了1,2,3-三唑类化合物的合成、表征、配位化学和缓蚀潜力。详细讨论了金属催化叠氮化物-炔环加成的各种方法，以及用于合成1,2,3-三唑基体系的无金属化学和基于有机催化剂的点击化学。对这些杂环化合物进行了系统的文献调查，这些杂环化合物在酸性、中性和盐水环境中对各种金属和合金（包括低碳钢、铜和铝）具有很强的抑制性能。本文还描述了三唑衍生物的配体性质，如非无害行为、给体、反给体、共振效应和配位模式，这些都促进了它们与金属d轨道的相互作用。总的来说，这项工作结合了1,2,3-三唑在腐蚀科学中的实际进展和化学基础，为开发下一代既环保又高效的抑制剂提供了建议。

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引用次数: 0

Theoretical investigation of the reaction mechanism for formation of pyridinyl formimidamide ancillary ligand in the synthesis of a new Class of iridium(III) complexes 一类新型铱（III）配合物合成中吡啶基甲咪酰胺辅助配体形成反应机理的理论研究

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-10-20 DOI: 10.1016/j.jorganchem.2025.123903

Nurul Husna As Saedah Bain , Noorshida Mohd Ali , David Robinson , Abu-Baker M. Abdel-Aal

In this study, density functional theory (DFT) calculations were performed to explore the reaction mechanism for the formation of a silver-formimidamide intermediate complex in the synthesis pathway of a novel cyclometallated iridium(III) complex bearing a pyridine-formimidamide ancillary ligand. The purpose of this study is to provide a detailed explanation of how the cyclic carbene ancillary ligand of (2-(4-methylbenzyl)-1H-1,2,4-triazol-1-yl)pyridine, MBpyta converted into acyclic (E)-N-cyano-N-(4-methylbenzyl)-N'-(pyridin-2-yl) formimidamide, CNMBpyfa when undergoing complexation with chloro-bridged iridium(III) dimer [{Ir(F₂ppy)₂(µ-Cl)}₂]. The calculated results showed that the role of silver(I) oxide and the electron-withdrawing effect of the starting ligand in reactants triggered the two stages of deprotonation of two carbons in the starting triazolium salt precursor. Geometrical optimization reveals that the crystal structure of complex Ir(F₂ppy)₂(CNMBpyfa) has the lowest electronic energy compared to other designated ancillary ligand positions, confirming that the experimental data represent the most stable state of the synthesized complex.

本研究通过密度泛函理论（DFT）计算，探讨了含吡啶-甲米酰胺辅助配体的新型环金属化铱（III）配合物合成途径中银-甲米酰胺中间配合物形成的反应机理。本研究的目的是详细解释（2-（4-甲基苄基）- 1h -1,2,4-三唑-1-酰基）吡啶的环羰基配体MBpyta在与氯桥接铱（III）二聚体[{Ir(F2ppy)2（µ- cl）}2]络合时如何转化为无环(E)- n-氰- n-（4-甲基苄基）- n '-（吡啶-2-酰基）甲米酰胺CNMBpyfa。计算结果表明，氧化银的作用和起始配体在反应物中的吸电子作用触发了起始三唑盐前驱体中两个碳的两阶段去质子化。几何优化表明配合物Ir(F2ppy)2（CNMBpyfa）的晶体结构与其他指定的辅助配体位置相比具有最低的电子能量，证实了实验数据代表了合成配合物最稳定的状态。

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引用次数: 0

Computational study on the copolymerization of α-olefins with polar monomer catalyzed by [N, P] Ti complexes: A DFT model for catalytic activity evaluation [N， P] Ti配合物催化α-烯烃与极性单体共聚的计算研究：催化活性评价的DFT模型

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-10-20 DOI: 10.1016/j.jorganchem.2025.123904

Jiaojiao Zhang , Wenwen Cong , Yi Li

A detailed theoretical mechanistic study on the α-olefins polymerization and copolymerization with polar monomers catalyzed by [N, P] Ti complexes is presented. This work primarily focuses on a computational investigation using density functional theory (DFT) to elucidate the relative free energies for various transition states and intermediates during the process of olefins copolymerization. The study examining key elementary steps, including chain initiation, chain propagation and chain termination (considering two potential pathways for the latter: β-hydride elimination and β-hydride transformation). The results indicate that the stability and steric bulk of the complexes can enhance the introduction of -F. For ethylene homo(co)polymerization, the introduction of one or more -F substituents on the backbone of the ligands tend to decrease the energy barriers. In contrast, variations in the substituents exert negligible effects on the activation barriers for ethylene/9-decen-1-ol copolymerization. A significant energy difference of approximately 8.8 kcal/mol was calculated between complexes bearing -CH₃ and -F substituents in the β-hydride elimination step. This relatively large energy span suggests a substantial influence on resulting polymer molecular weight. Collectively, these DFT calculations demonstrate the potential for predicting the activity of novel complexes within this family, thereby providing a valuable tool for designing new catalysts.

本文对[N， P] Ti配合物催化α-烯烃与极性单体聚合共聚的机理进行了详细的理论研究。本工作主要集中于利用密度泛函理论（DFT）的计算研究来阐明烯烃共聚过程中各种过渡态和中间体的相对自由能。该研究考察了关键的基本步骤，包括链起始、链传播和链终止（考虑了后者的两种可能途径：β-氢化物消除和β-氢化物转化）。结果表明，配合物的稳定性和立体体积有利于-F的引入。对于乙烯homo（co）聚合，在配体的主链上引入一个或多个-F取代基往往会降低能垒。相反，取代基的变化对乙烯/9-十二烯-1-醇共聚的激活障碍的影响可以忽略不计。在β-氢化物消除步骤中，携带-CH₃和-F取代基的配合物之间的能量差约为8.8 kcal/mol。这种相对较大的能量跨度表明对所得聚合物分子量有实质性的影响。总的来说，这些DFT计算证明了预测该家族中新型配合物活性的潜力，从而为设计新的催化剂提供了有价值的工具。

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引用次数: 0

Design and immobilized gold nanoparticles into the chitosan-xanthan gum polymers as a novel catalyst for efficient nitroarenes reduction in water 设计并将金纳米颗粒固定在壳聚糖-黄原胶聚合物中，作为水中高效还原硝基芳烃的新型催化剂

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-10-20 DOI: 10.1016/j.jorganchem.2025.123902

Narinderjit Singh Sawaran Singh , Ibrahim Saeed Gataa , Luma Hussain Saleh , M M Rekha , Subhashree Ray , Kattela Chennakesavulu , Renu Sharma , Wissam Aziz Yousif , Akmal Abilkasimov , Mutabar Latipova , M.A. Diab , Heba A. El-Sabban

This research presents an innovative method for designing and creating a polymeric composite platform derived from chitosan-xanthan gum polysaccharides (CS-XG) to encapsulate gold nanoparticles, leading to the development of a novel CS-XG/Au NPs nanocomposite. The CS-XG composite was formed through hydrogen bonding and further providing a natural framework that acts as a capping, reducing, and stabilizing agent for the formation of gold nanoparticles. The successful creation of the CS-XG/Au NPs was confirmed using a range of advanced analytical methodologies, including UV-Vis, FE-SEM, TEM, EDX, elemental mapping, XRD and ICP-OES. TEM images indicated that the gold nanoparticles were spherical in shape, monodispersed, and had an approximate size of 40-50 nm. Following the characterization of CS-XG/Au NPs, its catalytic activity were successfully utilized in the reduction of various nitroarenes in an aqueous medium. Notably, the catalyst can be simply recovered and reused for at least 8 successive cycles with minimal loss of catalytic performance, highlighting its promise for sustainable and practical uses in green chemistry.

本研究提出了一种创新的方法来设计和制造壳聚糖-黄原胶多糖（CS-XG）的聚合物复合平台，以封装金纳米粒子，从而开发出一种新的CS-XG/金纳米复合材料。CS-XG复合材料是通过氢键形成的，进一步提供了一个自然框架，作为金纳米颗粒形成的封盖、还原和稳定剂。CS-XG/Au NPs的成功创建使用了一系列先进的分析方法，包括UV-Vis， FE-SEM， TEM， EDX，元素映射，XRD和ICP-OES。TEM图像表明，金纳米颗粒呈球形，单分散，尺寸约为40-50 nm。在对CS-XG/Au NPs进行表征后，成功地利用了其在水介质中还原各种硝基芳烃的催化活性。值得注意的是，该催化剂可以简单地回收并重复使用至少8个连续循环，而催化性能的损失最小，突出了其在绿色化学中的可持续和实际应用前景。

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引用次数: 0

High-valent ruthenium oxo/dioxo complexes and their mechanistic insights 高价钌氧/二氧配合物及其机理研究

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-10-16 DOI: 10.1016/j.jorganchem.2025.123899

Manali Dutta

This review article chronicles a brief account of the oxidative carbon-carbon multiple bond cleavage reaction, the conventional and catalytic approaches and the drawbacks associated with these reactions. In this connection, the synthesis and characterization of various reported high-valent ruthenium-oxo/dioxo complexes and the indispensable roles played by these complexes in the oxidative transformation of alcohols, alkenes, alkynes and alkyl arenes have been described. The detailed mechanistic aspects of various ligand bound well defined high-valent ruthenium-oxo/dioxo intermediates and their utility as oxidant for variety of organic transformations have been discussed.

本文简要介绍了氧化碳-碳多键裂解反应、传统的裂解方法和催化的裂解方法以及这些反应的缺陷。在这方面，介绍了各种已报道的高价钌氧/二氧配合物的合成和表征，以及这些配合物在醇、烯烃、炔烃和烷基芳烃的氧化转化中所起的不可或缺的作用。详细的机制方面的各种配体结合明确的高价钌-氧/二氧中间体和它们的用途作为氧化剂的各种有机转化进行了讨论。

引用次数: 0

Homochirality and chiral recognition in ruthenium complexes of the type [NH2Et2][{RuCl(P-P)}2(μ-Cl)3] where P-P = bidentate phosphine [NH2Et2][{RuCl(P-P)}2(μ-Cl)3]型钌配合物的同手性和手性识别，其中P-P =双齿膦

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-10-14 DOI: 10.1016/j.jorganchem.2025.123897

J.W. Faller, Nikos Sarantopoulos, Jonathan Parr

The ions [(η⁶-cymene)Ru(μ-Cl)₃]⁻ and [L₂(X)Ru(μ-Cl)₃]^1-/2− are direct analogs of the Kläui ligands and we have used these ligands as components in preparing ruthenium dimers, including (η⁶-cymene)Ru(μ-Cl)₃Ru(BIPHEP)Cl. The conformations of the BIPHEP ligands in [NH₂Et₂][{RuCl(BIPHEP)}₂(μ-Cl)₃], however, have the potential of producing either homochiral (R,R) or (S,S) dimers or the (R,S) heterodimer. The crystal structure of this BIPHEP ruthenium complex shows a racemic mixture of (R,R) and (S,S) dimers, suggesting that the chirality in one half of the dimer strongly influences the stability of the chirality in the other half.

离子[（η - 6-花癸烯）Ru(μ-Cl)3]−和[L2(X)Ru(μ-Cl)3]1-/2−是Kläui配体的直接类似物，我们用这些配体作为组分制备钌二聚体，包括（η - 6-花癸烯）Ru(μ-Cl)3Ru(BIPHEP)Cl。然而，BIPHEP配体在[NH2Et2][{RuCl(BIPHEP)}2(μ-Cl)3]中的构象有可能产生同手性（R，R）或（S，S）二聚体或（R，S）异源二聚体。该BIPHEP钌配合物的晶体结构为（R，R）和（S，S）二聚体的外消旋混合物，表明二聚体中一半的手性强烈影响另一半手性的稳定性。

引用次数: 0