二价双烯酮亚胺基稀土金属配合物催化ε-己内酯开环聚合

近年来，以双烯酮亚胺基为辅助配体合成金属有机配合物已经引起了化学工作者的广泛关注，其中部分双烯酮亚胺基金属配合物显示出独特的催化反应性能。最近，我们以双烯酮亚胺基为辅助配体合成了一些金属有机配合物，发现具有较大空间位阻的双烯酮亚胺基是合成混配型稀土金属有机配合物的理想配体。进一步研究发现用Na-K合金还原混配型双烯酮亚胺基稀土金属氯化物，     

四氮唑-1-乙酸及其衍生物金属构筑配合物的研究进展

四氮唑-1-乙酸(Htza)类有机配体具有良好的配位能力和多样的配位形式,在配位化学领域得到了迅速且广泛的研究。本文总结了基于四氮唑-1-乙酸配体构筑的金属配合物的研究进展和这些金属配合物的结构特征,讨论了基于四氮唑-1-乙酸构筑的金属配合物在光学、磁性、催化方面的应用,并对这类配体的发展前景进行了展望。     

相转移催化合成N,N′-二(3,5-二甲基吡唑)烷

近年来,多齿含氮配体在金属有机配合物的合成和研究中日益受到重视,不仅用在高氧化态、缺电子中心的高价过渡金属有机配合物上,而且已开始在低氧化态、富电子中心的低价过渡金属有机配合物上应用,其中一个重要原因是自然界里许多的金属酶普遍含有以氮为配位原子的配体。因此,本文试图研究N,N′-二(3,5-二甲基吡唑)烷的合成。70年代初,Trofimenko 用3,5-二甲基     

不同配体的稀土金属配合物在烯烃聚合领域的研究进展

催化剂在推动聚烯烃工业发展中有着举足轻重的作用,其中金属催化剂的设计与合成更是金属有机催化化学的关键.稀土金属具有独特的轨道结构、反应活性和配位准则,因此稀土金属配合物通过在金属中心周围引入空间位阻,在聚烯烃材料制备中表现出独特优势.其中配体是决定稀土金属配合物的结构、化学活性及稳定性等方面的关键因素.本综述介绍了茂基配体(烷基取代、芳基取代、茚和芴配体)和非茂基配体(大环四齿配体、三齿配体、双齿配体和单齿配体)的稀土金属配合物的发展及其在聚烯烃制备中的应用.这项工作旨在促进稀土金属催化剂在聚烯烃催化和金属有机催化领域的研究,为高端化、差异化聚烯烃聚合催化剂的制备提供新的设计思路和研究方法.     

非平面分子内电荷转移离子配合物的合成及其光物理性质

以N-乙烯基咔唑三羰基铬为模板化合物, 选用丙烯基阳离子取代其中一个羰基配体, 合成了一种新型非平面分子内电荷转移有机金属配合物. 通过元素分析、红外、核磁共振确定了配合物的组成和结构, 电子吸收和荧光光谱结果表明配合物的光物理行为可通过配体取代调控．运用双光束前向简并四波混频(DFWM)的方法, 测试了配合物及配体的三阶非线性效应, 同时探讨了金属配位和配体取代对其的影响.     

一种新型的吡唑衍生物的合成

近年来,多齿含氮的配体在有机配合物的合成和研究中日益受到重视,不仅用在高氧化态、缺电子中心的高价过渡金属有机配合物上,而且已开始在低氧化态、富电子中心的低价过渡金属有机配合物上应用,其中一个重要原因是自然界中许多金属酶普遍含有以氮为配位原子的配体.我们合成了N,N'-二(3,5-二甲基吡唑)烷的衍生物1,同时分离得到了一种新型的环状化合物2.     

基于四齿配体的蓝光d8金属配合物及其OLED应用的研究进展

用于有机发光二极管(OLED)的红光和绿光磷光金属配合物材料在稳定性和发光效率方面均已达到了目前产业化应用的要求,而蓝光磷光配合物则在稳定性方面无法达到应用条件。高能量的激发态以及d-d态引起的配合物分解是造成蓝光磷光OLED器件稳定性差的原因之一。采用四齿配体开发d~8金属配合物是同时提升配合物发光效率和稳定性的途径之一,有望在蓝光磷光材料和器件应用方面取得突破。本文总结了基于四齿配体的蓝光铂(Ⅱ)和钯(Ⅱ)配合物的研究进展,通过探讨配体结构对配合物光物理性质和稳定性的影响,为继续开发具有应用前景的蓝光金属配合物材料提供了指导性方向。     

手性环戊二烯过渡金属配合物在不对称催化反应中的应用

手性环戊二烯配体作为不对称催化反应中的立体控制元素受到金属有机工作者的关注,尤其是设计合成更多通用的手性环戊二烯基配体成为了不对称催化领域的研究中心之一.综述了近年来发展出的各种手性环戊二烯配体与不同过渡金属的配合物,以及这些配合物在催化不对称反应方面的进展.     

环金属钌配合物的合成、结构多样性及氧化还原调控（英文）

环金属钌配合物具有良好的氧化还原和光物理性质,在诸多光电领域如染料敏化太阳能电池、电致变色、电子转移等方面具有重要应用.环金属钌配合物的合成方法主要包括"后期金属化"、"前期金属化"、"转金属化"三种方法.环金属配合物具有丰富的结构多样性.环金属配合物由环金属配体和辅基配体与金属螯合形成.环金属配体包括N^C、N^N^C、N^C^N和C^C^C-类型多齿配体.辅基配体主要包括吡啶、咪唑、三唑、嘧啶等杂环.碳-金属键的引入大大降低了钌配合物的氧化还原电位.通过改变环金属配体和辅基配体的结构,可以对金属的氧化还原电位进行有效调控.金属钌配合物的氧化还原电位对敏化电池的性能以及电子转移的过程具有重要的影响.     

巯基四氮唑衍生物构筑金属配合物的研究概况与展望

巯基四氮唑是一类具有丰富配位原子的有机硫配体,迄今,已报道的巯基四氮唑衍生物构筑的金属配合物种类繁多,结构新颖,可应用于生物、光电等诸多领域。本文分析了巯基四氮唑衍生物配体的配位特点并总结了其配位模式,并从单取代、双取代及多臂巯基四氮唑衍生物三个方面分别对巯基四氮唑构筑的金属配合物及其发展现状进行综述,同时简述了巯基四氮唑基配合物的生物活性及光电特性,最后对巯基四氮唑衍生物构筑金属配合物的前景进行了展望。     

Lipase active-site-directed anchoring of organometallics: metallopincer/protein hybrids

The work described herein presents a strategy for the regioselective introduction of organometallic complexes into the active site of the lipase cutinase. Nitrophenol phosphonate esters, well known for their lipase inhibitory activity, are used as anchor functionalities and were found to be ideal tools to develop a single-site-directed immobilization method. A small series of phosphonate esters, covalently attached to ECE "pincer"-type d8-metal complexes through a propyl tether (ECE=[C6H3(CH2E)(2)-2,6]-; E=NR2 or SR), were designed and synthesized. Cutinase was treated with these organometallic phosphonate esters and the new metal-complex/protein hybrids were identified as containing exactly one organometallic unit per protein. The organometallic proteins were purified by membrane dialysis and analyzed by ESI-mass spectrometry. The major advantages of this strategy are: 1) one transition metal can be introduced regioselectively and, hence, the metal environment can potentially be fine-tuned; 2) purification procedures are facile due to the use of pre-synthesized metal complexes; and, most importantly, 3) the covalent attachment of robust organometallic pincer complexes to an enzyme is achieved, which will prevent metal leaching from these hybrids. The approach presented herein can be regarded as a tool in the development of regio- and enantioselective catalyst as well as analytical probes for studying enzyme properties (e.g., structure) and, hence, is a "proof-of-principle design" study in enzyme chemistry.     

Main-chain organometallic polymers: synthetic strategies, applications, and perspectives

Main-chain organometallic polymers utilize transition metal-organic ligand complexes as primary components of their backbones. These hybrid materials effectively integrate the physical and electronic properties of organic polymers with the physical, electronic, optical, and catalytic properties of organometallic complexes. Combined with the rich and continuously growing array of ligands for transition metals, these materials have outstanding potential for use in a broad range of applications. This tutorial review discusses the major classes of main-chain organometallic polymers, including coordination polymers, poly(metal acetylide)s, and poly(metallocene)s. Emphasis is placed on their synthesis, characterization, physical properties, and applications, as well as ongoing challenges and limitations. These discussions are supplemented with highlights from the recent literature. The review concludes with perspectives on the current status of the field, as well as opportunities that lie just beyond its frontier.     

Deprotonative metalation using ate compounds: synergy, synthesis, and structure building

Historically, single-metal organometallic species such as organolithium compounds have been the reagents of choice in synthetic organic chemistry for performing deprotonation reactions. Over the past few years, a complementary new class of metalating agents has started to emerge. Owing to a variable central metal (magnesium, zinc, or aluminum), variable ligands (both in their nature and number), and a variable second metallic center (an alkali metal such as lithium or sodium), "ate" complexes are highly versatile bases that exhibit a synergic chemistry which cannot be replicated by the homometallic magnesium, zinc, or aluminum compounds on their own. Deprotonation accomplished by using these organometallic ate complexes has opened up new perspectives in organic chemistry with unprecedented reactivities and sometimes unusual and unpredictable regioselectivities.     

Planar chiral (η5-cyclohexadienyl)- and (η6-arene)-tricarbonylmanganese complexes: synthetic routes and application

Planar chiral arenetricarbonylchromium complexes have been intensively investigated and they have been applied as valuable building blocks for asymmetric synthesis and as ligands for asymmetric catalysis. In contrast, in the field of the isoelectronic cationic [(η(6)-arene)Mn(CO)(3)](+) complexes, until these last 10 years, very few studies were published involving nonracemic planar chiral cationic complexes and their potential applications, certainly because of the difficult access to enantiopure starting material. In 2009, however, the discovery of the first resolution of such compounds opened a new area for their application in the field of organic as well as of organometallic enantioselective syntheses. We felt it important to write a review on this subject to give an up-to-date summary of the methodologies used to prepare enantiomerically pure planar chiral neutral [(η(5)-cyclohexadienyl)Mn(CO)(3)] and cationic [(η(6)-arene)Mn(CO)(3)](+) complexes as well as their potential in enantioselective synthesis.     

Organotransition-metal chemistry: past development and future outlook

The course of the development of organometallic chemistry is reviewed from the author's personal viewpoint. The impact of the discoveries of ferrocene and the Ziegler catalyst on the later development of organotransition-metal chemistry is discussed. Through evolution of fundamental concepts, such as the insertion of olefins and carbon monoxide into metal—carbon bonds, oxidative addition and reductive elimination, and attack of nucleophiles on coordinated ligands, together with reactivities of carbene and metallacyclic complexes, various important processes have been developed. The diversity of transition-metal complexes and their unique reactivities not found in usual organic compounds warrant further developments in the various forefronts related to organometallic chemistry with almost limitless possibilities in applications as well as in fundamental studies.     

Optically active organometallic compounds (a personal account from the inside)

Results of a long experience of our group in Moscow in the area of chiral organometallic stereochemistry are described. They embrace optically active organometallic derivatives of mercury, palladium, platinum, functionalized ferrocenes, ruthenocenes, and cymantrenes as well as less common objects such as organometallic fullerenes and the cyclodextrin-metallocenes inclusion complexes.     

Benzodiazepines: Drugs with Chemical Skeletons Suitable for the Preparation of Metallacycles with Potential Pharmacological Activity

The synthesis of organometallic compounds with potential pharmacological activity has attracted the attention of many research groups, aiming to take advantage of aspects that the presence of the metal-carbon bond can bring to the design of new pharmaceutical drugs. In this context, we have gathered studies reported in the literature in which psychoactive benzodiazepine drugs were used as ligands in the preparation of organometallic and metal complexes and provide details on some of their biological effects. We also highlight that most commonly known benzodiazepine-based drugs display molecular features that allow the preparation of metallacycles via C-H activation. These organometallic compounds merit further attention regarding their potential biological effects, not only in terms of psychoactive drugs but also in the search for drug replacements, for example, for cancer treatments.     

The chemistry of (1-azabuta-1,3-diene)tricarbonyliron(0) complexes

In this review, an overview of synthetic and structural aspects of 1-azabuta-1,3-diene complexes of iron is given and the reactivity of these complexes is discussed with regard to inorganic, organometallic, organic and stereochemical aspects of their chemistry. Their application in the synthesis of organic and organometallic target compounds, or as transfer reagents of the tricarbonlyiron(0) moiety is demonstrated.     

固体表面金属有机化合物的结构及其性质

表面金属有机化学是近年来一个快速发展的新研究领域。通过这种思想和方法所合成出的表面金属有机化合物具有明确的结构和特殊的性质,在催化研究和材料制备中有着广泛的应用,国内外已经进行了大量的研究并取得了许多非常有价值的结果。本文引用了40余篇文献侧重评述了氧化物、金属、沸石等固体表面金属有机化合物的结构和性质。     

芳基钌抗癌化合物的研究进展

无机药物化学领域正在快速发展,尤其是有机金属配合物作为癌症的治疗和诊断试剂有很大的潜力.芳基钌配合物中芳基对抗癌活性有重要影响,并能调控配合物金属中心的热力学和动力学性能.配合物的构效关系研究,对进一步合理设计/合成具有潜在药用价值的有机金属配合物至关重要.本文选取钌芳基配合物作为抗癌药物的具体实例进行讨论,重点介绍了多种芳基钌配合物的构效关系及抗癌机理.