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Difunctionalization Processes Enabled by Hexafluoroisopropanol 六氟异丙醇促成的双官能化过程
Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-03-04 DOI: 10.1021/acsorginorgau.3c00067
Maciej Piejko, Joseph Moran* and David Lebœuf*, 

In the past 5 years, hexafluoroisopropanol (HFIP) has been used as a unique solvent or additive to enable challenging transformations through substrate activation and stabilization of reactive intermediates. In this Review, we aim at describing difunctionalization processes which were unlocked when HFIP was involved. Specifically, we focus on cyclizations and additions to alkenes, alkynes, epoxides, and carbonyls that introduce a wide range of functional groups of interest.

在过去 5 年中,六氟异丙醇(HFIP)作为一种独特的溶剂或添加剂,通过激活底物和稳定反应中间体,实现了具有挑战性的转化。在本综述中,我们将介绍在 HFIP 参与下实现的双官能化过程。具体来说,我们将重点介绍烯烃、炔烃、环氧化物和羰基的环化和加成反应,这些反应引入了各种相关的官能团。
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引用次数: 0
(Electro)chemical N2 Splitting by a Molybdenum Complex with an Anionic PNP Pincer-Type Ligand (钼配合物与阴离子 PNP 钳型配体的(电)化学 N2 裂解作用
Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-03-04 DOI: 10.1021/acsorginorgau.3c00056
Nils Ostermann, Nils Rotthowe, A. Claudia Stückl and Inke Siewert*, 

Molybdenum(III) complexes bearing pincer-type ligands are well-known catalysts for N2-to-NH3 reduction. We investigated herein the impact of an anionic PNP pincer-type ligand in a Mo(III) complex on the (electro)chemical N2 splitting ([LMoCl3], 1, LH = 2,6-bis((di-tert-butylphosphaneyl)methyl)-pyridin-4-one). The increased electron-donating properties of the anionic ligand should lead to a stronger degree of N2 activation. The catalyst is indeed active in N2-to-NH3 conversion utilizing the proton-coupled electron transfer reagent SmI2/ethylene glycol. The corresponding Mo(V) nitrido complex 2H exhibits similar catalytic activity as 1H and thus could represent a viable intermediate. The Mo(IV) nitrido complex 3 is also accessible by electrochemical reduction of 1 under a N2 atmosphere. IR- and UV/vis-SEC measurements suggest that N2 splitting occurs via formation of an “overreduced” but more stable [(L(N2)2Mo0)2μ-N2]2– dimer. In line with this, the yield in the nitrido complex increases with lower applied potentials.

带有钳型配体的钼(III)配合物是众所周知的 N2 到 NH3 还原催化剂。我们在此研究了钼(III)配合物中的阴离子 PNP 钳型配体对 N2(电)化学拆分([LMoCl3]-, 1-, LH = 2,6-双((二叔丁基膦烷基)甲基)-吡啶-4-酮)的影响。阴离子配体的电子供能特性的增强应导致更强的 N2 活化程度。利用质子耦合电子转移试剂 SmI2/乙二醇,该催化剂在 N2 到 NH3 的转化过程中确实具有活性。相应的 Mo(V)吡啶络合物 2H 表现出与 1H 类似的催化活性,因此可能是一种可行的中间体。在氮气环境下,通过电化学还原 1-,也可以得到钼(IV)吡啶配合物 3-。IR- 和 UV/vis-SEC 测量结果表明,N2 分离是通过形成 "过度还原 "但更稳定的 [(L(N2)2Mo0)2μ-N2]2- 二聚体来实现的。与此相一致的是,随着应用电位的降低,氮化物复合物的产率也会增加。
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引用次数: 0
ACS Organic & Inorganic Au’s 2023 Rising Stars Unveiled 美国化学学会有机与无机奥组委 2023 年度新星揭晓
Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-03-01 DOI: 10.1021/acsorginorgau.4c00012
Franc Meyer, P. Shiv Halasyamani and Géraldine Masson*, 
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引用次数: 0
Theoretical Photoelectron Spectroscopy of Metal–Metal Quintuple Bonds: Relativity-Driven Reordering of Frontier Orbitals 金属-金属五键的理论光电子能谱学:相对论驱动的前沿轨道重排
Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-03-01 DOI: 10.1021/acsorginorgau.4c00002
Abhik Ghosh*,  and , Jeanet Conradie*, 

A recent reinvestigation of the gas-phase photoelectron spectra of Group 6 metal–metal quadruple-bonded complexes with scalar-relativistic DFT calculations showed that common exchange-correlation functionals reproduce the lowest ionization potentials in a semiquantitative manner. The finding encouraged us to undertake a DFT study of metal–metal quintuple bonds in a set of bisamidinato complexes with the formula MI2[HC(NR)2]2 (M = Cr, Mo, W; R = H, Ph, 2,6-iPr2C6H3) and idealized D2h symmetry. Scalar-relativistic OLYP/STO-TZ2P calculations indicated significant shifts in valence orbital energies among the three metals, which translate to lower first ionization potentials, higher electron affinities, and lower HOMO–LUMO gaps for the W complexes relative to their Cr and Mo counterparts. These differences are largely attributable to substantially larger relativistic effects in the case of tungsten relative to those of its lighter congeners.

最近通过标量相对论 DFT 计算对第 6 族金属-金属四键配合物的气相光电子能谱进行了重新研究,结果表明常见的交换相关函数以半定量的方式再现了最低电离电位。这一发现鼓励我们对一组双脒基配合物中的金属-金属五键进行 DFT 研究,这些配合物的化学式为 MI2[HC(NR)2]2(M = Cr、Mo、W;R = H、Ph、2,6-iPr2C6H3),对称性为理想化的 D2h。标量相对论 OLYP/STO-TZ2P 计算表明,这三种金属的价轨道能量发生了显著变化,因此相对于 Cr 和 Mo 复合物而言,W 复合物的第一电离电位更低、电子亲和力更高、HOMO-LUMO 间隙更小。这些差异在很大程度上归因于钨相对于其较轻同系物的更大相对论效应。
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引用次数: 0
Zinc(II) Complexes of SIRTi1/2 Analogues Transmetallating with Copper Ions and Inducing ROS Mediated Paraptosis SIRTi1/2 类似物的锌(II)配合物与铜离子透射并诱导 ROS 介导的猝灭作用
Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-02-26 DOI: 10.1021/acsorginorgau.3c00052
Ashwini Kumar, Ayushi Chaudhary, Himanshu Sonker, Seemadri Subhadarshini, Mohit K. Jolly and Ritika Gautam Singh*, 

As the SIRTi analogue series (HL1–HL6) show potent antitumor activity in vitro, we synthesized their corresponding zinc(II) complexes (ZnL1–ZnL6) and investigated their potential as anticancer agents. The Zn(II) complexes showed substantially greater cytotoxicity than HL1–HL6 alone in several cancer cell-types. Notably, distinct structure–activity relationships confirmed the significance of tert-butyl (ZnL2) pharmacophore inclusion in their activity. ZnL2 complexes were found to transmetalate with copper ions inside cells, causing the formation of redox-active copper complexes that induced reactive oxygen species (ROS) production, mitochondrial membrane depolarization, ATP decay, and cell death. This is the first study to exhibit Zn(II) complexes that mediate their activity via transmetalation with copper ions to undergo paraptosis cell death pathway. To further confirm if the SIRT1/2 inhibitory property of SIRTi analogues is conserved, a docking simulation study is performed. The binding affinity and specific interactions of the Cu(II) complex obtained after transmetalation with ZnL2 were found to be higher for SIRT2 (Ki = 0.06 μM) compared to SIRT1 (Ki = 0.25 μM). Thus, the concurrent regulation of several biological targets using a single drug has been shown to have synergistic therapeutic effects, which are crucial for the effective treatment of cancer.

由于 SIRTi 类似物系列(HL1-HL6)在体外显示出强大的抗肿瘤活性,我们合成了相应的锌(II)配合物(ZnL1-ZnL6),并研究了它们作为抗癌剂的潜力。与 HL1-HL6 本身相比,锌(II)配合物在几种癌细胞类型中显示出更强的细胞毒性。值得注意的是,独特的结构-活性关系证实了叔丁基(ZnL2)药理结构在其活性中的重要作用。研究发现,ZnL2 复合物能在细胞内与铜离子发生金属化反应,形成具有氧化还原作用的铜复合物,诱导活性氧(ROS)产生、线粒体膜去极化、ATP 衰减和细胞死亡。这是首次有研究表明,锌(II)复合物通过与铜离子发生跨金属化作用来介导其活性,从而实现细胞旁突变死亡途径。为了进一步证实 SIRTi 类似物的 SIRT1/2 抑制特性是否是保守的,我们进行了对接模拟研究。研究发现,与 SIRT1(Ki = 0.25 μM)相比,与 ZnL2 反金属化后得到的 Cu(II) 复合物对 SIRT2 的结合亲和力和特异性相互作用更高(Ki = 0.06 μM)。因此,使用一种药物同时调节多个生物靶点已被证明具有协同治疗效果,这对有效治疗癌症至关重要。
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引用次数: 0
Manipulating the Rate and Overpotential for Electrochemical Water Oxidation: Mechanistic Insights for Cobalt Catalysts Bearing Noninnocent Bis(benzimidazole)pyrazolide Ligands 操纵电化学水氧化的速率和过电位:对含有非无害双(苯并咪唑)吡唑配体的钴催化剂的机理认识
Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-02-14 DOI: 10.1021/acsorginorgau.3c00061
Yu-Ting Wu, Sharad V. Kumbhar, Ruei-Feng Tsai, Yung-Ching Yang, Wan-Qin Zeng, Yu-Han Wang, Wan-Chi Hsu, Yun-Wei Chiang*, Tzuhsiung Yang*, I-Chung Lu* and Yu-Heng Wang*, 

Electrochemical water oxidation is known as the anodic reaction of water splitting. Efficient design and earth-abundant electrocatalysts are crucial to this process. Herein, we report a family of catalysts (13) bearing bis(benzimidazole)pyrazolide ligands (H2L1H2L3). H2L3 contains electron-donating substituents and noninnocent components, resulting in catalyst 3 exhibiting unique performance. Kinetic studies show first-order kinetic dependence on [3] and [H2O] under neutral and alkaline conditions. In contrast to previously reported catalyst 1, catalyst 3 exhibits an insignificant kinetic isotope effect of 1.25 and zero-order dependence on [NaOH]. Based on various spectroscopic methods and computational findings, the L3Co2III(μ-OH) species is proposed to be the catalyst resting state and the nucleophilic attack of water on this species is identified as the turnover-limiting step of the catalytic reaction. Computational studies provided insights into how the interplay between the electronic effect and ligand noninnocence results in catalyst 3 acting via a different reaction mechanism. The variation in the turnover-limiting step and catalytic potentials of species 13 leads to their catalytic rates being independent of the overpotential, as evidenced by Eyring analysis. Overall, we demonstrate how ligand design may be utilized to retain good water oxidation activity at low overpotentials.

电化学水氧化被称为阳极水分裂反应。高效设计和富土电催化剂对这一过程至关重要。在此,我们报告了一系列含有双(苯并咪唑)吡唑配体(H2L1-H2L3)的催化剂(1-3)。H2L3 含有电子捐赠取代基和非无辜成分,因此催化剂 3 表现出独特的性能。动力学研究表明,在中性和碱性条件下,[3] 和 [H2O] 具有一阶动力学依赖性。与之前报道的催化剂 1 不同,催化剂 3 的动力学同位素效应为 1.25,与[NaOH]的关系为零。根据各种光谱方法和计算发现,L3Co2III(μ-OH) 物种被认为是催化剂的静止态,水对该物种的亲核攻击被认为是催化反应的转化限制步骤。计算研究深入揭示了电子效应和配体非长效性之间的相互作用如何导致催化剂 3 通过不同的反应机制发挥作用。正如艾林分析所证明的那样,物种 1-3 的转化限制步骤和催化电位的变化导致它们的催化速率与过电位无关。总之,我们展示了如何利用配体设计在低过电位下保持良好的水氧化活性。
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引用次数: 0
Recent Advances on the Catalytic Asymmetric Allylic α-Alkylation of Carbonyl Derivatives Using Free Allylic Alcohols 使用游离烯丙基醇催化羰基衍生物的不对称烯丙基α-烷基化的最新进展
Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-02-10 DOI: 10.1021/acsorginorgau.3c00065
Diego A. Alonso, Beatriz Maciá, Isidro M. Pastor and Alejandro Baeza*, 

During the last years, the development of more sustainable and straightforward methodologies to minimize the generation of waste organic substances has acquired high importance within synthetic organic chemistry. Therefore, it is not surprising that many efforts are devoted to ameliorating already well-known successful methodologies, that is, the case of the asymmetric allylic allylation reaction of carbonyl compounds. The use of free alcohols as alkylating agents in this transformation represents a step forward in this sense since it minimizes waste production and the substrate manipulation. In this review, we aim to gather the most recent methodologies describing this strategy by paying special attention to the reaction mechanisms, as well as their synthetic applications.

在过去几年中,开发更可持续、更简单的方法以尽量减少废弃有机物的产生在有机合成化学中占据了重要地位。因此,许多人致力于改进已经众所周知的成功方法,如羰基化合物的不对称烯丙基烯丙基化反应,也就不足为奇了。在这一转化过程中使用游离醇作为烷基化剂,是在这一意义上向前迈出的一步,因为它最大限度地减少了废物的产生和底物的操作。在这篇综述中,我们旨在收集描述这种策略的最新方法,特别关注反应机理及其合成应用。
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引用次数: 0
Biomimetic Frustrated Lewis Pair Catalysts for Hydrogenation of CO to Methanol at Low Temperatures 低温下将 CO 加氢转化为甲醇的仿生受挫路易斯对催化剂
Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-01-31 DOI: 10.1021/acsorginorgau.3c00064
Jiejing Zhang, Longfei Li*, Xiaofeng Xie, Xue-Qing Song* and Henry F. Schaefer III*, 

The industrial production of methanol through CO hydrogenation using the Cu/ZnO/Al2O3 catalyst requires harsh conditions, and the development of new catalysts with low operating temperatures is highly desirable. In this study, organic biomimetic FLP catalysts with good tolerance to CO poison are theoretically designed. The base-free catalytic reaction contains the 1,1-addition of CO into a formic acid intermediate and the hydrogenation of the formic acid intermediate into methanol. Low-energy spans (25.6, 22.1, and 20.6 kcal/mol) are achieved, indicating that CO can be hydrogenated into methanol at low temperatures. The new extended aromatizationdearomatization effect involving multiple rings is proposed to effectively facilitate the rate-determining CO 1,1-addition step, and a new CO activation model is proposed for organic catalysts.

使用 Cu/ZnO/Al2O3 催化剂通过 CO 加氢法工业生产甲醇需要苛刻的条件,因此开发具有低操作温度的新型催化剂非常必要。本研究从理论上设计了对 CO 毒物具有良好耐受性的有机仿生 FLP 催化剂。无碱催化反应包括 CO 与甲酸中间体的 1,1-加成反应和甲酸中间体加氢转化为甲醇的反应。该反应实现了低能量跨度(25.6、22.1 和 20.6 kcal/mol),表明一氧化碳可在低温下氢化成甲醇。该研究提出了涉及多个环的新的扩展芳香化-脱芳香化效应,从而有效地促进了决定速率的 CO 1,1- 加成步骤,并为有机催化剂提出了一个新的 CO 活化模型。
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引用次数: 0
On the Ytterbium Valence and the Physical Properties in Selected Intermetallic Phases 某些金属间化合物中的镱价和物理性质
Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-01-04 DOI: 10.1021/acsorginorgau.3c00054
Stefan Engel, Elias C. J. Gießelmann, Maximilian K. Reimann, Rainer Pöttgen* and Oliver Janka*, 

The present review summarizes important aspects of the crystal chemistry of ytterbium-based intermetallic compounds along with a selection of their outstanding physical properties. These originate in many cases from the ytterbium valence. Different valence states are possible here, divalent (4f14), intermediate-valent, or trivalent (4f13) ytterbium, resulting in simple diamagnetic, Pauli or Curie–Weiss paramagnetic, or valence fluctuating behavior. Especially, some of the Yb3+ intermetallics have gained deep interest due to their Kondo or heavy Fermion ground states. We have summarized their property investigations using magnetic and transport measurements, specific heat data, NMR, ESR, and Mössbauer spectroscopy, elastic and inelastic neutron scattering, and XAS data as well as detailed thermoelectric measurements.

本综述总结了镱基金属间化合物晶体化学的一些重要方面,以及它们的一些突出物理性质。在许多情况下,这些特性源于镱的价态。二价(4f14)、中价或三价(4f13)镱的不同价态可能导致简单的二磁性、保利或居里-魏斯顺磁性或价态波动行为。特别是一些 Yb3+ 金属间化合物因其近藤基态或重费米子基态而引起了人们的浓厚兴趣。我们利用磁性和传输测量、比热数据、核磁共振、ESR 和莫斯鲍尔光谱、弹性和非弹性中子散射、XAS 数据以及详细的热电测量,总结了它们的性质研究。
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引用次数: 0
Synthesis of Indolyl Phenyl Diketones through Visible-Light-Promoted Ni-Catalyzed Intramolecular Cyclization/Oxidation Sequence of Ynones 通过可见光促进的镍催化 Ynones 分子内环化/氧化顺序合成吲哚基苯基二酮类化合物
Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-12-21 DOI: 10.1021/acsorginorgau.3c00060
Yufeng Zhou, Yaping Wang, Peidong Xu, Weiwei Han, Heng-Ying Xiong* and Guangwu Zhang*, 

The combination of visible light catalysis and Ni catalysis has enabled the synthesis of indolyl phenyl diketones through the cyclization/oxidation process of ynones. This reaction proceeded under mild and base-free conditions and showed a broad scope and feasibility for gram-scale synthesis. Several natural products and biologically interesting molecules could be readily postfunctionalized by this method.

将可见光催化与镍催化相结合,通过炔酮的环化/氧化过程合成了吲哚基苯基二酮。该反应在温和、无碱的条件下进行,为克级合成提供了广阔的空间和可行性。通过这种方法,一些天然产物和具有生物学意义的分子可以很容易地进行后官能化。
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引用次数: 0
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ACS Organic & Inorganic Au
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