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碳十硼烷及其衍生物的反应性及应用 总被引:1,自引:0,他引:1
碳十硼烷(C2B10H12)是由2个C原子和10个B原子组成的二十面体笼状结构大分子,有邻位、间位和对位三种异构体。碳十硼烷庞大的体积以及类芳香族三维刚性结构使它具有优异的高温稳定性和化学稳定性,良好的溶解性使其具有广泛而灵活的应用。本文总结了近年来碳十硼烷和碳十硼烷衍生物在C原子、B原子上的化学反应性以及在环加成和金属络合方面的研究。另外,由于碳十硼烷衍生物特殊的立体结构,优异的耐高温性、热氧化性及高硼含量,本文综述了碳十硼烷衍生物近年来在功能材料、催化剂及生物医药等多个领域的应用进展。 相似文献
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邻碳硼烷及其所衍生的邻碳硼炔化合物能够与多种不饱和化合物发生环加成反应转化为结构新颖的功能碳硼烷衍生物.这些功能碳硼烷衍生物在硼中子捕获疗法、催化合成、药物设计等诸多领域都有着广阔的应用前景.近年来,人们在邻碳硼烷和邻碳硼炔的官能化领域取得了显著成就,尤其在反应条件优化、反应选择性控制、反应机理研究等方面取得了明显进步.对近十年以来国内外课题组在邻碳硼烷与炔烃、烯烃、多环或杂环芳烃等不饱和化合物的环加成反应领域所取得的实验研究成果进行了总结,并对邻碳硼炔参与的[2+2+2]、[2+2+1]、[2+2]、[3+2]、[4+2]、[5+2]等环加成反应的实验和理论研究成果、尤其是反应机理作了详细介绍,最后对该领域的发展前景进行了展望. 相似文献
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十二顶点碳硼烷是一类含有碳、氢及硼原子的簇合物,具有特殊的热稳定性和化学稳定性,在医药、材料、能源、配位化学及金属有机化学中都得到广泛的应用.近年来,过渡金属催化的碳硼烷直接硼-氢键活化发展迅速,为硼顶点选择性官能团化提供了一系列新的高效路径.总结了利用过渡金属催化硼-氢键活化策略来实现邻碳硼烷硼-硼、硼-氮、硼-氧、硼-硫及硼-卤键构建的研究进展,同时对部分反应机理进行了讨论,并就该研究领域所面临的挑战和发展前景进行了展望. 相似文献
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碳硼烷是一类由两个碳氢及十个硼氢顶点组成的笼状分子,在医学、材料、配位化学和金属有机化学等领域都有重要的应用,因此发展高效、简便的方法高选择性获取碳硼烷官能化衍生物具有重要的理论和现实意义.近年来,通过亲电取代、过渡金属催化、亲核取代等策略,实现了碳硼烷硼–氢键高效、高选择性官能化.本文根据硼–氢键的不同反应位点,评述了利用亲核取代反应策略进行碳硼烷选择性官能团化的研究进展,详细讨论了反应底物普适性、选择性控制及反应机理,并对该领域后续研究所面临的挑战和发展前景进行了展望. 相似文献
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从1963年发现闭二碳代十二硼烷[Carborane(C_2B_(10) H_(12) ,下简称碳十硼烷)]以来,碳硼烷化学得到了迅速的发展,它不但在理论上有重要意义,而且已经在实际上得到了应用,特别是作为耐高温、耐辐射(吸收中子)的合成材料,脑瘤放射治疗以及作为固体推进剂组分. 相似文献
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The bioinorganic and medicinal chemistry of carboranes: from new drug discovery to molecular imaging and therapy 总被引:1,自引:0,他引:1
The role of carboranes in medicinal chemistry has diversified in recent years and now extends into areas of drug discovery, molecular imaging, and targeted radionuclide therapy. An introduction to carborane chemistry is provided to familiarize the non-expert with some key properties of these molecules, followed by an overview of current medicinally-orientated research involving carboranes. The broad-ranging nature of this research is illustrated, with emphasis placed on recent highlights and advances in this field. 相似文献
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The chemistry of boron clusters has been dominated by icosahedral carboranes for over half a century. Only in recent years has significant progress been made in the chemistry of supercarboranes (carboranes with more than 12 vertices). A number of CAd (carbon‐atoms‐adjacent) 13‐ and 14‐vertex carboranes, and CAp (carbon‐atoms‐apart) 13‐vertex carboranes as well as their corresponding 14‐ and 15‐vertex metallacarboranes have been successfully prepared and structurally characterized. This breakthrough relied on the use of CAd nido‐carborane dianions as starting materials. These supercarboranes can undergo single‐electron reduction to give stable supercarborane radical monoanions with [2n+3] framework electrons, and electrophilic substitution reaction to afford hexasubstituted supercarboranes. They can react with nucleophiles to offer monocarba‐closo‐dodecaborate monoanions from cage‐carbon extrusion reactions. Their unique chemical properties make the chemistry of supercarboranes distinct from that of their 12‐vertex analogues. These studies open up new possibilities for the development of polyhedral clusters of extraordinary size. This focus review offers an overview of recent advances in this growing research field. 相似文献
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Xiang Li Prof. Dr. Hong Yan Prof. Dr. Qiang Zhao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(6):1888-1898
Phosphorescent transition‐metal complexes (PTMCs) have attracted great interest because of their excellent properties which may lead to promising applications in optoelectronics. In recent years, carboranes have been demonstrated to be a novel and effective tool to tune phosphorescence of PTMCs. This Concept article deals with the advances of carborane‐functionalized PTMCs for potential optical applications. The discussions are focused on the design strategies and synthetic procedures leading to carborane‐functionalized PTMCs, the influence of carboranes on the optical properties of PTMCs, and the promising optical applications of this interesting class of phosphorescent materials. 相似文献
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The review concerns the synthesis, structure, and chemical transformations of mercury derivatives of various polyhedral boron hydrides (carboranes, metallacarboranes, and boranes) and covers a period of time since the pioneering studies of Prof. V. I. Bregadze on chemistry of C- and B-substituted derivatives of icosahedral carboranes C2B10H12 up to date. The emphasis is placed on recent results obtained in this field, in particular, Hg-promoted substitution in nido-carboranes as well as the synthesis and properties of mercury derivatives of monocarbon carborane anion [CB11H12]–.
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Vincent Terrasson Dr. José Giner Planas Dr. Damien Prim Prof. Francesc Teixidor Prof. Dr. Clara Viñas Prof. Dr. Mark E. Light Dr. Michael B. Hursthouse Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(44):12030-12042
The convenient synthesis of original aminobenzyl‐o‐carboranes, which represent a new class of nitrogenated carborane derivatives, is described. These novel compounds have been efficiently prepared starting from commercially available aromatic aldehydes and monosubstituted o‐carboranes via carboranyl alcohols and chlorides as intermediates. The key step of this methodology is a selective nucleophilic amination under mild conditions that allows the formation of the expected amines while limiting the partial deboronation of the carborane cluster. This general strategy has been applied to the preparation of a wide variety of aminobenzyl‐o‐carboranes. The extension of this pathway to the synthesis of enantiopure carborane–amine combinations is also described. 相似文献
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The protonation of chloroethane by the strongest known solid superacid, the carborane acid H(CHB(11)Cl(11)), has been studied by quantitative IR spectroscopic methods to track mass balance and uncover previously unobserved chemistry. In the first step, an intermediate EtCl·H(CHB(11)Cl(11)) species without full proton transfer to EtCl can be observed when d(5)-deuterated chloroethane is used. It rapidly eliminates HCl (but not DCl) to form ethyl carborane, Et(CHB(11)Cl(11)), which binds a second molecule of chloroethane to form the Et(2)Cl(+) chloronium ion. This undergoes a slower, previously unrecognized HCl elimination reaction to form a butyl carborane, Bu(CHB(11)Cl(11)), beginning an oligomerization process whereby unsymmetrical dialkylchloronium ions decompose to alkyl carboranes of formula Bu(C(2)H(4))(n)(CHB(11)Cl(11)) up to n = 4. Over time, a parallel competing process of de-oligomerization take place in the presence of free carborane acid that finishes with the formation of hexyl or butyl carboranes. Upon heating to 150 C, the final products are all converted to the remarkably stable tert-butyl cation carborane salt. 相似文献
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Da Zhao Jiji Zhang Prof. Dr. Zuowei Xie 《Angewandte Chemie (International ed. in English)》2014,53(32):8488-8491
Like the importance of benzyne, witnessed in modern arene chemistry for decades, 1,2‐dehydro‐o‐carborane (o‐carboryne), a three‐dimensional relative of benzyne, has been used as a synthon for generating a wide range of cage, carbon‐functionalized carboranes over the past 20 years. However, the selective B functionalization of the cage still represents a challenging task. Disclosed herein is the first example of 1,3‐dehydro‐o‐carborane featuring a cage C? B bond having multiple bonding characters, and is successfully generated by treatment of 3‐diazonium‐o‐carborane tetrafluoroborate with non‐nucleophilic bases. This presents a new methodology for simultaneous functionalization of both cage carbon and boron vertices. 相似文献
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Aggregation‐Induced Delayed Fluorescence Based on Donor/Acceptor‐Tethered Janus Carborane Triads: Unique Photophysical Properties of Nondoped OLEDs
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In Seob Park Jiyoung Lee Prof. Dr. Takuma Yasuda 《Angewandte Chemie (International ed. in English)》2016,55(25):7171-7175
Luminescent materials consisting of boron clusters, such as carboranes, have attracted immense interest in recent years. In this study, luminescent organic–inorganic conjugated systems based on o‐carboranes directly bonded to electron‐donating and electron‐accepting π‐conjugated units were elaborated as novel optoelectronic materials. These o‐carborane derivatives simultaneously possessed aggregation‐induced emission (AIE) and thermally activated delayed fluorescence (TADF) capabilities, and showed strong yellow‐to‐red emissions with high photoluminescence quantum efficiencies of up to 97 % in their aggregated states or in solid neat films. Organic light‐emitting diodes utilizing these o‐carborane derivatives as a nondoped emission layer exhibited maximum external electroluminescence quantum efficiencies as high as 11 %, originating from TADF. 相似文献
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The presence of boron atoms has made carboranes, C(2)B(10)H(12), attractive candidates for boron neutron capture therapy. Because of their chemistry and possible conjugation with proteins, they can also be used to enhance interactions between pharmaceuticals and their targets and to increase the in vivo stability and bioavailability of compounds that are normally metabolized rapidly. Carboranes are isosteric to a rotating phenyl group, which they can substitute successfully in biologically active systems. A reverse ligand-protein docking approach was used in this work to identify binding proteins for carboranes. The screening was carried out on the drug target database PDTD that contains 1207 entries covering 841 known potential drug targets with structures taken from the Protein Data Bank. First, for validation, the protocol was applied to three crystal structures of proteins in which carborane derivatives are present. Then, the model was applied to systems for which the protein structure is available, but the binding site of carborane has not been reported. These systems were used for further validation of the protocol, while simultaneously providing new insight into the interactions between cage and protein. Finally, the screening was carried out on the database to reveal potential carborane binding targets of interest for biological and pharmacological activity. Carboranes are predicted to bind well to protease and metalloprotease enzymes. Other carborane pharmaceutical targets are also discussed, together with possible protein carriers. 相似文献
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Following a discussion of bonding, the structures of the known carboranes of the clovo type and of the incompletely condensed types are described; the recently discovered carboranes with high carbon contents, such as tetracarbahexaborane (“boracarbane”) are also discussed. The preparation of carboranes from polyboranes and the possibility of obtaining organo carboranes from organoboranes are then described. Some rearrangements which take place within the carborane skeleton are also mentioned. 相似文献