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Ligand K-Edge XAS Studies of Metal-Phosphorus Bonds: Applications, Limitations, and Opportunities 金属-磷键的配体K-Edge XAS研究:应用、限制和机遇
IF 5.4 3区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2018-03-04 DOI: 10.1080/02603594.2018.1465938
Courtney M. Donahue, Scott R. Daly
Phosphorus K-edge X-ray absorption spectroscopy (XAS) is a highly effective experimental method for investigating metal-phosphorus bonding and electronic structure. Here, we provide a comprehensive review of P K-edge XAS studies of transition metal complexes and show how they were used to investigate a wide range of chemical phenomena, including covalent metal-ligand bonding, redox non-innocence in ligands, molecular magnetism, and luminescence. Limitations of the technique are discussed along with opportunities for future work.
磷k边x射线吸收光谱(XAS)是研究金属-磷键和电子结构的有效实验方法。在这里,我们全面回顾了过渡金属配合物的P - k边缘XAS研究,并展示了它们如何用于研究广泛的化学现象,包括共价金属-配体键、配体中的氧化还原非无罪、分子磁性和发光。讨论了该技术的局限性以及未来工作的机会。
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引用次数: 6
Commentary on the Synthesis and Structures of Unsupported Cycloarsoxane Compounds 非负载型环胂烷化合物的合成及结构评述
IF 5.4 3区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2018-01-05 DOI: 10.1080/02603594.2018.1423618
Mutasem Z. Bani-Fwaz, A. Fazary
This comment describes the available synthetic routes and some general structural features of unsupported cycloarsoxane compounds. The key synthetic strategies used to prepare this type of compound and the significant roles that they have been employed in after coordination to the metal center are fully discussed. The literature herein covers all known unsupported cycloarsoxane compounds that have been structurally characterized by X-ray diffraction techniques.
本文介绍了无负载环胂烷化合物的合成路线和一些一般结构特征。详细讨论了制备该类化合物的关键合成策略及其与金属中心配位后所起的重要作用。本文的文献涵盖了所有已知的用x射线衍射技术进行结构表征的无负载环胂烷化合物。
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引用次数: 4
All That Glitters Is Not Gold: A Computational Study of Covalent vs Metallophilic Bonding in Bimetallic Complexes of d10 Metal Centers—A Tribute to Al Cotton on the Tenth Anniversary of His Passing 所有闪光的都不是黄金:d10金属中心双金属配合物中共价与亲金键的计算研究——致敬Al Cotton逝世十周年
IF 5.4 3区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2018-01-02 DOI: 10.1080/02603594.2018.1467315
Brooke M. Otten, Kortney M Melancon, M. Omary
As the tenth year that follows the premature passing of the inorganic chemistry legend F. Albert (Al) Cotton comes to a close, we provide some soul food that we believe Al would have enjoyed as he looks down upon two generations of disciples, a grandchild and two great grandchildren, in his scientific family tree. This article also represents a new tradition by which the editors of Comments on Inorganic Chemistry wish to lead by example, whereby we start publishing original research content that nonetheless preserves the journal’s identity as a niche for “critical discussion of the current literature” of inorganic chemistry. Thus, we show novel demonstrations of a posteriori validation and a priori prediction of possible counterintuitive covalent M-M’ bonds—after and before synthesis, respectively—contrasted with non-covalent M···M interactions of the metallophilic type in bridge-dimeric systems of d10 metal centers. Mixing of (n + 1)s0/p0 orbitals with (n)d10 orbitals in the former heterobimetallics case—and lack thereof in the latter homobimetallics case—is hypothesized to be responsible for the presence or absence of covalency, respectively. However, we also demonstrate that the consequent d-s’ and/or d-p’ orbital mixing/hybridization can occur even in homobimetallic complexes that contain asymmetric bridging ligands (e.g., with -S^C- donor atoms that lead to orbital interactions between M-S and M-C fragments). Hence, the “control” metallophilic case for the hypothesized d10-d10 polar-covalent bonding herein is best manifest by M2(P^P)2 homobimetallics vis-à-vis M2(S^C)2 embodiments. Finally, we also offer a point/counterpoint commentary to the readers to contrast factors that argue for covalency vs metallophilicity and forewarn against exaggerating the extent of covalent bonding in such d10-d10 species. Thus, scrutinizing the various theoretical parameters has pointed to M-M’ and M-M partially bonded S^C-bridge dinuclear d10 complexes vis-à-vis the classic Cotton-type multiple metal-metal bond description in d0
无机化学传奇人物f·阿尔伯特·科顿(F. Albert (Al) Cotton)英年早逝的第十个年头即将结束,我们提供了一些灵魂食物,我们相信,当阿尔在他的科学家谱中俯视两代弟子,一个孙子和两个曾孙时,他一定会享受到这些食物。这篇文章也代表了《无机化学评论》的编辑们希望以身作则的新传统,即我们开始发表原创研究内容,但仍保留了该杂志作为无机化学“当前文献批判性讨论”的定位。因此,我们展示了对可能的反直觉共价M-M键的事后验证和先验预测,分别在合成后和合成前,与d10金属中心的桥式二聚体体系中亲金型的非共价M···M相互作用进行了对比。在前一种异相金属的情况下,(n + 1) 0/p0轨道与(n)d10轨道的混合,以及在后一种均相金属的情况下的缺乏,被假设分别是共价存在或不存在的原因。然而,我们也证明了d-s '和/或d-p '轨道混合/杂化甚至可以发生在含有不对称桥接配体的同双金属配合物中(例如,与-s ^C-供体原子导致M-S和M-C片段之间的轨道相互作用)。因此,本文假设的d10-d10极性共价键的“控制”亲金性情况最好通过M2(P^P)2均相金属物与-à-vis M2(S^C)2实施例相体现。最后,我们还为读者提供了一个观点/对位评论,以对比共价性与亲金性的争论因素,并警告不要夸大此类d10-d10物种的共价键的程度。因此,仔细研究各种理论参数,指出M-M '和M-M部分成键的S^ c桥双核d10配合物与-à-vis中经典的棉花型多金属-金属键描述
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引用次数: 10
EOV Editoral Board EOV编辑委员会
IF 5.4 3区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2017-11-02 DOI: 10.1080/02603594.2017.1399689
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引用次数: 0
Performance Vs Convenience of Magnetic Carbon-Metal Nanocomposites: A Low-Cost and Facile Citrate-Derived Strategy for Feco Alloy/Carbon Composites with High-Performance Microwave Absorption 磁性碳-金属纳米复合材料的性能与便利性:一种低成本、易于使用的柠檬酸盐衍生feo合金/碳复合材料的高性能微波吸收策略
IF 5.4 3区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2017-10-02 DOI: 10.1080/02603594.2017.1374257
Wenlei Chu, Chunhua Tian, Ying Wang, Jiayu Chu, Zhigang Li, Yunchen Du, Xijiang Han
Magnetic carbon-based composites reside at the frontier of high-performance microwave absorbing materials (MAMs) due to their dual loss mechanisms and tunable electromagnetic properties. In this study, we review the construction of magnetic carbon-metal composites in recent years, and introduce a facile citrate-derived strategy to produce FeCo alloy/carbon composites through a direct pyrolysis of the resultant gels, where citric acid is employed as both a carbon source and a complexing agent. It is found that the dosage of citric acid determines the crystalline phase and particle size of magnetic FeCo alloy particles, as well as the content of carbon components. Electromagnetic analysis indicates that the electromagnetic functions of these composites are highly dependent on their specific compositions, where carbon components favor high complex permittivity and FeCo alloy particles take charge of complex permeability. When the chemical composition is optimized, good attenuation ability and characteristic impedance matching are created in the composite, resulting in desirable microwave absorption properties. The absorption performance is comparable to most homologous composites reported. Considering the low-cost and easy preparative process, we believe that this citrate-derived strategy may be instructive and helpful for practical applications of various magnetic carbon-based composites in the field of microwave absorption. Graphical Abstract
磁性碳基复合材料由于具有双重损耗机制和可调谐的电磁特性,处于高性能吸波材料的前沿。在这项研究中,我们回顾了近年来磁性碳-金属复合材料的结构,并介绍了一种简单的柠檬酸衍生策略,通过直接热解所得凝胶来生产FeCo合金/碳复合材料,其中柠檬酸作为碳源和络合剂。研究发现,柠檬酸的用量决定了磁性FeCo合金颗粒的晶相和粒度,以及碳组分的含量。电磁分析表明,这些复合材料的电磁功能高度依赖于它们的特定成分,其中碳成分有利于高复介电常数,而FeCo合金颗粒负责复磁导率。当化学成分优化后,复合材料具有良好的衰减能力和特性阻抗匹配,从而获得理想的微波吸收性能。吸收性能与大多数同类复合材料相当。考虑到制备工艺简单、成本低,我们相信这种柠檬酸盐衍生的策略对各种磁性碳基复合材料在微波吸收领域的实际应用具有指导意义和帮助。图形抽象
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引用次数: 12
Methane Manifesto: A Theorist’s Perspective on Catalytic Light Alkane Functionalization 甲烷宣言:催化轻烷烃功能化的理论家视角
IF 5.4 3区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2017-09-03 DOI: 10.1080/02603594.2016.1242487
T. Cundari
The catalytic functionalization of light alkanes, particularly methane, has attracted considerable attention from the inorganic and organic research communities for nearly five decades. The literature mechanisms for C—H activation may be divided into three broad categories: metal directed, ligand directed, or metal-ligand directed. The advantages for metal-ligand directed pathways have both steric and electronic origins. Furthermore, computations suggest that the stereoelectronic requirements for the activation and functionalization component reactions can be diametrically opposed. From this research, several questions emerge for theorists that would aid in the hunt for synthesizable complexes for efficient catalytic functionalization of light alkanes. First, is there a happy medium by which a complex is nucleophilic enough to activate a alkane C—H bond with a reasonable rate, but that is not so basic as to thwart the subsequent C—O,N bond-forming step? Second, what are the energetic consequences of moving along the “ide”/“yl” continuum? Third, how can the electronic coupling among the three main catalyst components—metal, actor ligand, and spectator ligand—be modulated to permit the use of Earth-abundant catalysts to effect catalytic functionalization of light alkanes?
近五十年来,轻烷烃特别是甲烷的催化功能化引起了无机和有机研究界的广泛关注。C-H活化的文献机制可分为三大类:金属定向、配体定向或金属-配体定向。金属配体定向途径的优点有空间和电子来源。此外,计算表明,激活和功能化组分反应的立体电子要求可以完全相反。从这项研究中,理论家们提出了几个问题,这些问题将有助于寻找可合成的配合物,以实现轻烷烃的有效催化功能化。首先,是否存在一种令人满意的介质,使络合物具有足够的亲核性,能够以合理的速率激活烷烃碳氢键,但又不至于碱性到阻碍随后的碳氧氮键形成步骤?第二,沿着“ide”/“yl”连续体移动的能量后果是什么?第三,如何调节三种主要催化剂组分(金属、参与者配体和旁观者配体)之间的电子耦合,以允许使用地球上丰富的催化剂来实现轻烷烃的催化功能化?
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引用次数: 5
Mechanistic Aspects of Copper-Catalyzed Decarboxylative Coupling Reactions of (Hetero)Aryl Carboxylic Acids 铜催化(杂)芳基羧酸脱羧偶联反应机理研究
IF 5.4 3区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2017-07-04 DOI: 10.1080/02603594.2016.1261023
J. Hoover
Copper-catalyzed oxidative decarboxylative coupling reactions of benzoic acids have emerged as attractive routes to access functionalized arenes. Unfortunately, substrate scope limitations and forcing reaction conditions have prevented the widespread implementation of these methodologies. A mechanistic understanding of these systems could enable the development of more robust reactions, yet few studies have targeted the mechanistic elucidation of these complex systems. This article reviews the copper-catalyzed decarboxylation reactions of hetero(aromatic) acids, including protodecarboxylations, redox-neutral decarboxylative couplings, and oxidative decarboxylative coupling reactions. We emphasize the mechanistic insights learned from each system to build a framework for understanding copper-catalyzed decarboxylative coupling reactions.
铜催化苯甲酸的氧化脱羧偶联反应已成为获得功能化芳烃的重要途径。不幸的是,衬底范围的限制和强制反应条件阻碍了这些方法的广泛实施。对这些系统的机制理解可以使更强大的反应的发展,但很少有研究针对这些复杂系统的机制阐明。本文综述了铜催化的杂芳香酸脱羧反应,包括原脱羧反应、氧化还原-中性脱羧偶联反应和氧化脱羧偶联反应。我们强调从每个系统中获得的机理见解,以建立一个理解铜催化脱羧偶联反应的框架。
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引用次数: 16
Holmium for Use in Cancer Therapy 钬用于癌症治疗
IF 5.4 3区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2017-06-12 DOI: 10.1080/02603594.2017.1333498
Yi Shi, A. Johnsen, A. D. Di Pasqua
Over the last few decades, holmium (Ho) has been investigated for its application in laser surgery, magnetic resonance imaging, and internal and topical radionuclide therapy. Ho has a 100% natural abundance of holmium-165, which is a stable nuclide that can undergo a process called neutron-activation to generate radioactive holmium-166 (166Ho). 166Ho emits β–particles and γ photons, with a half-life of 26.8 h; β–particles can damage a cancer cell’s DNA, while γ photons allow for 166Ho to be imaged in vivo and easily quantitated prior to, or during, dosing. This article gives a thorough account of the work being done around the world on 166Ho for use as an internal or topical radionuclide therapy against cancer. Our research group and others have generated compelling data that support the use of 166Ho as a radiotherapeutic in the clinic, especially since pharmaceutical formulations can be made while non-radioactive (Ho) and then made radioactive (166Ho) just prior to use. Graphical Abstract
在过去的几十年里,人们对钬(Ho)在激光手术、磁共振成像以及内部和局部放射性核素治疗中的应用进行了研究。Ho的天然丰度为100%,这是一种稳定的核素,可以经历一个称为中子活化的过程,产生放射性的钬-166 (166Ho)。166Ho发射β粒子和γ光子,半衰期为26.8 h;β -粒子可以破坏癌细胞的DNA,而γ光子允许166Ho在体内成像,并且在给药前或给药期间容易定量。本文全面介绍了世界各地关于166Ho作为抗癌内用或外用放射性核素治疗的工作。我们的研究小组和其他人已经产生了令人信服的数据,支持在临床中使用166Ho作为放射治疗药物,特别是因为药物配方可以在非放射性(Ho)的情况下制成,然后在使用之前制成放射性(166Ho)。图形抽象
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引用次数: 7
Strategies for Tuning Emission Energy in Phosphorescent Ir(III) Complexes 调节磷光Ir(III)配合物发射能量的策略
IF 5.4 3区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2017-05-04 DOI: 10.1080/02603594.2016.1207064
A. Huckaba, M. Nazeeruddin
Graphical Abstract Research into phosphorescent Ir(III) complexes has grown immensely since their first report. Talented chemists have successfully synthesized complexes capable of emitting from the ultraviolet to the near-infrared regions of the electromagnetic spectrum. Tuning the emission energy in a selective manner requires knowledge of how ligand substitution affects not only energy levels such as the highest occupied molecular orbital and lowest unoccupied molecular orbital, but also the emissive triplet energy level. This review describes fundamental principles involved in energy-level engineering and substituent selection as well as fundamental methods of device characterization.
自首次报道以来,对磷光Ir(III)配合物的研究得到了极大的发展。天才的化学家已经成功地合成了能够从电磁波谱的紫外线到近红外区域发射的配合物。以选择性方式调整发射能量需要了解配体取代如何不仅影响诸如最高已占据分子轨道和最低未占据分子轨道等能级,而且还影响发射三重态能级。本文介绍了能级工程和取代基选择的基本原理以及器件表征的基本方法。
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引用次数: 27
Hybrid Antioxidant and Metal Sequestering Small Molecules Targeting the Molecular Features of Alzheimer’s Disease 靶向阿尔茨海默病分子特征的混合抗氧化剂和金属螯合小分子
IF 5.4 3区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2017-05-04 DOI: 10.1080/02603594.2016.1241616
K. Green, Hannah M. Johnston, Marianne E. Burnett, Samantha M. Brewer
Graphical Abstract Alzheimer’s disease currently affects over 5.4 million Americans with $236 billion spent annually on the direct costs of patient care. Health experts expect this price tag to rise to $1.1 trillion by 2050 if intervention for disease progression is not found. Alzheimer’s disease is the sixth leading cause of death in the U.S. and the only disease in the top 10 causes of death that cannot currently be prevented or slowed. Of these deaths, two-thirds of Alzheimer’s disease victims are women. These statistics reflect an immediate worldwide need to understand the series of mechanisms that give rise to Alzheimer’s disease. With this understanding, we can develop therapeutic interventions for the disease. Here, we will discuss a selection of small molecules that have been recently developed to target the known molecular features of Alzheimer’s disease: amyloid-beta protein and oxidative stress. These potential therapeutics include small molecules inspired by early therapeutic potential demonstrated by the molecule clioquinol as well as divergent work that combines other metal-binding and antioxidant building blocks into one scaffold. The results related to the molecular features of Alzheimer’s disease will be presented.
阿尔茨海默病目前影响着540多万美国人,每年用于患者护理的直接费用为2360亿美元。卫生专家预计,如果无法找到针对疾病进展的干预措施,到2050年,这一费用将升至1.1万亿美元。阿尔茨海默病是美国第六大死亡原因,也是目前十大死亡原因中唯一无法预防或减缓的疾病。在这些死亡病例中,三分之二的阿尔茨海默病患者是女性。这些统计数据反映了全世界迫切需要了解引起阿尔茨海默病的一系列机制。有了这样的认识,我们就可以开发出针对这种疾病的治疗干预措施。在这里,我们将讨论最近开发的针对阿尔茨海默病已知分子特征的小分子:淀粉样蛋白和氧化应激。这些潜在的治疗方法包括由分子氯喹诺所展示的早期治疗潜力启发的小分子,以及将其他金属结合和抗氧化构建块结合成一个支架的不同工作。有关阿尔茨海默病的分子特征的结果将被提出。
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引用次数: 2
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Comments on Inorganic Chemistry
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