迷人的五元稀土金属循环王国

IF 16.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Wei Liu, Dajiang Huang, Junnian Wei and Wen-Xiong Zhang*, 
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引用次数: 0

摘要

金属环是碳环化合物的衍生物,其中金属原子取代了至少一个碳中心,在有机合成中一直是一个恒定的动力。虽然主族金属、过渡金属和锕系金属的金属循环已经被广泛研究,但那些含有稀土元素(Sc、Y和镧系元素)的金属循环仍然难以捉摸,主要是由于合成方面的挑战。然而,这些元素的正电特性和由此产生的RE - c键的极化,以及金属环内固有的协同效应,赋予了RE金属环独特的性质和丰富的,但在很大程度上尚未开发的反应化学。本文介绍了五元稀土金属循环的发展和应用。在过去的十年中,我们成功地合成了多种五元全碳稀土金属循环,采用了两种关键的合成策略:(1)金属转移,制备了稀土金属环戊二烯和螺环金属环戊二烯,它们具有不同的配体体系,在稀土中心周围提供了不同的配位环境,显著影响了它们的反应性;(2)金属转移和还原,使稀土金属环戊烯和2-丁烯四阴离子(BTA)桥接双核稀土金属环戊烯得以合成。还原过程通过金属环戊二烯的自歧化或二价稀土中心或碱金属的还原进行。这些金属环是此类含稀土金属环结构的第一个实例。我们对这些金属循环的研究发现了独特的反应活性和新的反应模式。稀土金属环的高本禀活性和多活性位点使其不仅能有效地激活小分子,而且对某些小分子表现出不同的激活模式。例如,稀土金属环戊二烯与碳二亚胺的反应表现出不同的插入/重排化学反应,受碳二亚胺等价物数量和溶剂选择等多种因素的影响。稀土金属环戊二烯介导的白磷[3 + 1]破碎表现出与主基团和过渡金属类似物明显不同的激活模式。此外,RE中心的交叉碳离子偶联和RE金属介导的苯开环复分解的发现引入了新的反应模式,表明通过合理的设计,RE金属可以表现出类似甚至超过过渡金属的性能。这些反应模式进一步促进了稀土金属循环在合成化学中的应用。此外,由于其独特的几何和电子结构,这些稀土金属环的一些新性质已经被发现。结构分析和理论计算揭示了bta桥接双核稀土金属环戊烯的非平面芳构性,将非平面芳构性的概念推广到碳-稀土金属环的化学中。此外,得益于丁二烯离子和BTA配体的氧化还原能力,BTA桥接的双核稀土金属环戊烯的配体氧化还原化学表现出多样化和高效的多电子转移过程,突出了这些金属环在氧化还原化学中的潜力。稀土金属环的结构、表征、性质、反应性和合成应用等方面的研究极大地丰富了f嵌段金属环的研究领域。我们希望这篇文章能激发人们进一步探索新的有机金属试剂的合成和金属环介导的转化,推动稀土化学的持续发展。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Enchanting Realm of Five-Membered Rare-Earth Metallacycles

Metallacycles, derivatives of carbocyclic compounds wherein a metal atom replaces at least one carbon center, have been a constant powerhouse in organic synthesis. While metallacycles of main-group, transition, and actinide metals have been extensively studied, those incorporating rare-earth (RE) elements (Sc, Y, and lanthanides) have remained elusive primarily due to synthetic challenges. Nevertheless, the electropositive character of these elements and the resulting polarization of RE–C bonds, along with the intrinsic synergistic effects within metallacycles, endow RE metallacycles with unique properties and a rich, yet largely untapped, reaction chemistry. In this Account, we present the development and applications of five-membered RE metallacycles.

Over the past decade, we have successfully synthesized a variety of five-membered all-carbon rare-earth metallacycles using two key synthetic strategies: (i) transmetalation, which has been employed to prepare RE metallacyclopentadienes and spiro-metallacyclopentadienes, which, featuring various ligand systems, provide distinct coordination environments around the RE center, significantly influencing their reactivity, and (ii) transmetalation and reduction, enabling the synthesis of RE spiro-metallacyclopentenes and 2-butene tetraanion (BTA)-bridged dinuclear RE metallacyclopentenes. The reduction process proceeds via either self-disproportionation of metallacyclopentadienes or reduction by divalent RE centers or alkali metals. These metallacycles represent the first instances of such RE-containing metallacyclic ring structures.

Our investigations into these metallacycles have uncovered unique reactivities and new reaction modes. The high intrinsic reactivity and multiple reactive sites of rare-earth metallacycles enable them not only to activate small molecules efficiently but also to exhibit distinct activation modes for some small molecules. For instance, reactions of RE metallacyclopentadienes with carbodiimides showcase diverse insertion/rearrangement chemistry, influenced by various factors such as number of equivalents of carbodiimide and the solvent choice. The RE metallacyclopentadiene-mediated [3 + 1] fragmentation of white phosphorus demonstrates an activation mode markedly different from that observed with main-group and transition metal analogs. Moreover, the discovery of cross-carbanion coupling at RE centers and RE-metal-mediated ring-opening metathesis of benzene introduces new reaction modes, demonstrating that, with rational design, RE metals can exhibit properties similar to or even surpassing those of transition metals. These reaction modes have further led to the development of applications for RE metallacycles in synthetic chemistry.

Additionally, some novel properties of these rare-earth metallacycles have been uncovered, stemming from their unique geometric and electronic structures. Structural analysis and theoretical calculations have revealed the nonplanar aromaticity of BTA-bridged dinuclear RE metallacyclopentenes, extending the concept of nonplanar aromaticity into the chemistry of carbon–RE metallacycles. Furthermore, benefiting from the redox capabilities of butadiene dianion and BTA ligands, the ligand-based redox chemistry of BTA-bridged dinuclear RE metallacyclopentenes demonstrates diverse and efficient multielectron transfer processes, highlighting the potential of these metallacycles for redox chemistry.

The studies of rare-earth metallacycles, encompassing their construction, characterization, properties, reactivity, and synthetic applications, have greatly enriched the field of f-block metallacycles. We hope that this Account will inspire further exploration into the synthesis of new organometallic reagents and metallacycle-mediated transformations, fueling continued progress in rare-earth chemistry.

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来源期刊
Accounts of Chemical Research
Accounts of Chemical Research 化学-化学综合
CiteScore
31.40
自引率
1.10%
发文量
312
审稿时长
2 months
期刊介绍: Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance. Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.
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