多核羰基钴配合物的合成及其催化活性的研究

多核羰基钴配合物对很多有机化学反应有良好的催化作用,从而引起人们很大关注.但这类配合物由高压反应得到,因此给实用带来不便. 我们通过各种含膦配体的氯化钴,在锌粉存在下,与一氧化碳在常温常压下反应,得到了一系列通式为:(PR_3)_mCo_n(CO)_x的多核羰基钴配合物,讨论了它们的结构,并对这些配合物在由十四碳烯羰基合成作为表面活性剂原料的十五碳伯醇反应中的催化性能进行了研究.     

氮杂环卡宾催化二氧化碳羧化反应的研究进展

二氧化碳是一种来源丰富的可再生资源,科研工作者一直致力于开发能够高效转化二氧化碳的催化体系。氮杂环卡宾在有机化学中是一类非常重要的催化剂,利用氮杂环卡宾-过渡金属配合物催化实现二氧化碳的高效化学转化受到了人们的广泛关注。本文主要根据氮杂环卡宾-过渡金属配合物进行分类,总结归纳了近年来氮杂环卡宾-过渡金属配合物催化二氧化碳羧化反应的研究进展。     

对DNA具有识别和断裂功能的金属插入剂的研究

本文详尽介绍了国际上对金属配合物与DNA 以插入方式进行识别和反应的前瞻性的工作,为设计能够与特定序列的DNA 进行识别和反应的金属配合物提供了多种策略。     

二价钴配合物催化烯烃氢硅化反应的机制研究

正J.Am.Chem.Soc.2017,139,1798~1801廉价金属催化在经济和资源可持续利用方面具有潜在优势,但对廉价金属催化反应的机制缺乏深入了解是制约廉价金属催化进一步快速发展的瓶颈.近年来,人们发现一些二价铁钴配合物可在无外加活化试剂存在下催化烯烃的氢硅化反应,但对于该类催化剂的反应机理认识不清.中国科学院上海有机化学研究所邓亮课题组研究发现,胺     

Mn-PNP催化碳酸亚乙酯氢化制甲醇的机理研究

催化氢化CO₂及其衍生物转化为高值化学品甲醇符合“绿色化学”的理念，是CO₂资源利用中最具应用前景的方法之一.本文基于密度泛函理论系统阐明了PNP配位的金属Mn配合物催化CO₂衍生物——碳酸亚乙酯氢化的反应机制.计算结果表明，Mn-PNP首先与氢气反应生成活性催化剂，接着碳酸亚乙酯在Mn—H和N—H物种的协助下经历3次氢化过程得到产物甲醇和副产物乙二醇，其中可能涉及outer-sphere和inner-sphere 2种反应机理，后者的总反应势垒为107.9 kJ·mol^-1,比前者低了27.0 kJ·mol^-1.催化氢化反应沿着inner-sphere路径进行更有利，这可能归因于inner-sphere路径有稳定中间体CH₃O—Mn配合物的形成.进一步探究了配体的取代基效应对金属Mn配合物催化活性的影响，证实强供电子能力的咪唑基团能够增加金属Mn中心的电子密度，一方面不利于Mn—H成键，另一方面可以提高Mn—H物种的亲核性.研究结果为筛选有效催化CO     

橙皮苷及其4种金属配合物与牛血清白蛋白结合作用的研究

合成了4种橙皮苷的金属配合物,采用紫外-可见、荧光光谱法研究了橙皮苷4种金属配合物与牛血清白蛋白(BSA)的相互作用。由Stern-Volmer方程和双倒数曲线Lineweaver-Burk方程获得了反应的动态猝灭常数、静态猝灭常数,从而判断出橙皮苷-锌与BSA作用机理为静态猝灭,其它配合物与BSA的作用为动态猝灭。并用热力学方法对结合反应的作用力类型做出了推断,橙皮苷-锌与BSA之间的作用力为静电作用。并得出了橙皮苷金属配合物与血清白蛋白作用的结合常数、结合位点数。同时采用同步荧光光谱法研究了橙皮苷金属配合物对BSA构象的影响。     

金属胶束模拟过氧化氢酶的热动力学研究

本文以金属胶束作为过氧化氢酶的模拟模型化合物，利用热动力学半寿期法分别研究了Fe^Ⅲ-trien金属配合物和Fe^Ⅲ-trien配合物分别与CTAB、SDS、Brij35等表面活性剂形成的金属胶束催化过氧化氢分解反应的热动力学。实验结果表明：Fe^Ⅲ-trien金属配合物与CTAB形成的金属胶束对过氧化氢分解反应有催化作用，而与SDS和Brij35形成的金属胶束对反应有禁阻作用。     

过渡金属膦配合物在硅氢化反应中的应用研究

过渡金属膦配合物在有机合成和催化反应中的应用非常广泛, 大量含膦杂原子配体被设计合成, 利用其特定的配位能力, 和过渡金属配位成过渡金属膦配合物, 并测试其对特定有机化学反应的催化性能. 硅氢加成反应是有机硅化学中的重要反应, 多种过渡金属包括铂、钯、铑、钌等的膦配合物对于硅氢加成反应均有催化活性. 综述了近几年来过渡金属膦配合物在硅氢加成反应中的应用进展.     

氮杂环卡宾配位的两配位二价钴亚胺基配合物:合成、结构与反应性质

<正>Angew.Chem.Int.Ed.2015,54,12640~12644低配位过渡金属配合物因其在小分子活化和单分子磁性方面的潜在价值而获得研究者的广泛关注.已知金属配合物的最低配位数是两配位,其中金属-配体多为σ-单键.最近,中国科学院上海有机化学研究所邓亮课题组采用大位阻的氮杂环卡宾和大位阻芳基亚胺基为配体实现了两配位钴-亚胺基配合物的合成.该配合物是首例含钴-主族元素多重键的两配位配合物.单晶X射线衍射、核磁氢谱、溶液相磁矩、理论计算等表明化合物自旋基态S=3/2.这一高自旋低配位钴亚胺基配合物可与一氧化碳作用发生乃春转移反应生成异氰酸酯,与乙烯反应生成乙醛亚胺,与     

甲醛与HCoN~2(PPh~3)~3的一个新反应

自从Roper等人在1979年合成了第一个锇的甲醛配合物Os(η~2-CH_2O)(CO)_2(PPh_3)_2以来,Fe、Ir、V等过渡金属配合物与甲醛反应的研究结果相继报道.这些工作对研究一氧化碳的加氢机理有着十分重要的意义.甲醛的氢甲酰化合成乙二醇在C_1化学中是一个值得开展的研究课题.因此,甲醛在过渡金属配合物上反应性质的研究与寻找有效的甲醛氢甲酰化催化剂密切相关. Misono等人在1968年报道过甲醛与HCoN_2(PPh_3)_3(1)发生了脱羰基反应,得到钴的     

Carbonylations of Alkenes with CO Surrogates

Alkene carbonylation reactions are important for the production of value‐added bulk and fine chemicals. Nowadays, all industrial carbonylation processes make use of highly toxic and flammable carbon monoxide. In fact, these properties impede the wider use of carbonylation reactions in industry and academia. Hence, performing carbonylations without the use of CO is highly desired and will contribute to the further advancement of sustainable chemistry. Although the use of carbon monoxide surrogates in alkene carbonylation reactions has been reported intermittently in the last 30 years, only recently has this area attracted significant interest. This Minireview summarizes carbonylation reactions of alkenes using different carbon monoxide surrogates.     

Nickel-Catalysed Reactions of Allyl Halides and Related Compounds

Allyl compounds react with carbon monoxide, or with carbon monoxide and acetylene, in the presence of tetracarbonylnickel as catalyst. These catalysts are involved also in coupling reactions and addition reactions of activated olefins and ketones. Reactions of this type can be used for the preparation of unsaturated aliphatic acids, esters, nitriles, hydrocarbons, alicyclic ketones, keto acids, keto esters, diketones, lactones, phenols, and other compounds. The reactions proceed via π-allylnickel complexes.     

Homogeneous catalysis by ruthenium carbonyl clusters

The historical background of and the incentive for using ruthenium carbonyl clusters as homogeneous catalysts are outlined. Keeping in view the possible solutions the uncertainties arising from declusterification and metal colloid formation are discussed. All ruthenium cluster-catalysed reactions are broadly classified as reactions with or without carbon monoxide as one of the reactants and the basic differences between such reactions are highlighted. Some of the factors of special relevance to cluster-catalysed reaction systems are mentioned. The reactions involving carbon monoxide are then discussed. These include water-gas-shift reaction, carbon monoxide hydrogenation, hydroformylation, reductive carbonylation of nitrobenzene and other carbonylation reactions. Hydrogenation, transfer hydrogenation, isomerisation and a few other reactions are then discussed. For all these reactions, special emphasis is laid on well-characterised cluster complexes that have been proposed as catalytic intermediates. Finally an attempt has been made to identify the path that future research in cluster catalysis is likely to follow.     

一氧化碳参与不饱和烃类化合物羰基化反应的研究进展

不饱和烃类化合物的羰基化反应是指在过渡金属催化剂存在条件下, 将一氧化碳(CO)分子以羰基的形式插入到烯烃(或者炔烃)与不同的亲核试剂中, 合成更高附加值化学品的转化过程. 本文综合评述了羰基化反应合成高附加值化学品的重要性, 介绍了几种不同类型的羰基化反应(氢甲酰化反应、 氢酯化反应、 氢酰胺化反应和氢羧基化反应)在发展新型催化剂体系及高效合成目标产物方面的研究进展, 并对羰基化反应存在的问题及未来发展方向和趋势进行了展望.     

Dinitrogen Activation and Addition to Unsaturated C−E (E=C,N, O,S) Bonds Mediated by Transition Metal Complexes

Dinitrogen (N₂) activation and functionalization is of fundamental interest and practical importance. This review focuses on N₂ activation and addition to unsaturated substrates, including carbon monoxide, carbon dioxide, heteroallenes, aldehydes, ketones, acid halides, nitriles, alkynes, and allenes, mediated by transition metal complexes, which afforded a variety of N−C bond formation products. Emphases are placed on the reaction modes and mechanisms. We hope that this work would stimulate further explorations in this challenging field.     

Catalytic Reactions with Hydrosilane and Carbon Monoxide [New synthetic methods (30)]

The reagent hydrosilane/carbon monoxide opens up new possibilities for organic synthesis. Four cases will be discussed: 1. The reaction of olefins with hydrosilane (trialkylsilane) and carbon monoxide in the presence of Co, Ru, and Rh complexes leads to enol silyl ethers having one more carbon atom that the olefins. 2. Cyclic ethers underto carbonylative ring opening to ω-siloxyaldehydes when reacted with hydrosilane and carbon monoxide in the presence of Co₂(CO)₈ as catalysts 3. Aldehydes are catalytically converted into the next higher α-siloxyaldehydes or 1,2-bis(siloxy)alkenes depending on the reaction conditions used. 4. The reaction of alkyl acetates proceeds in various ways depending on the nature of the alkyl group; enol silyl ethers or alkenes are optained.–Mechanisms of these Co₂(CO)₈ catalyzed reactions using hydrosilane and carbon monoxide are discussed in which HCo(CO)_n or R₃SiCo(CO)_nL function as catalytically active agents. With these species there are four types of catalytic cycles.–The synthetic possibilities of these catalytic reactions have still not been fully explored.     

Methylenecyclopropane as C1 synthetic units: [1+4] cycloaddition via a nickel catalyst

Nickel-catalyzed reactions of methylenecyclopropanes and thioanhydrides afford sulfur-containing heterocyclic compounds via [1+4] cycloaddition. The reactions represent a new use for methylenecyclopropane as a possible one-carbon building block to replace carbon monoxide, isocyanides, and Fischer carbene complexes.     

A safe and mild synthesis of organic carbonates from alkyl halides and tetrabutylammonium alkyl carbonates

A safe and mild procedure for the synthesis of mixed organic carbonates is described. Reaction of commercially available tetrabutylammonium methoxide and ethoxide with carbon dioxide yields the corresponding methyl and ethyl tetrabutylammonium carbonates (TBAMC and TBAEC). The reactions of these new compounds with several different alkyl halides give methyl and ethyl carbonates in high yields. The use of classic toxic and harmful chemicals such as phosgene and carbon monoxide is avoided.     

An Operando FTIR Spectroscopic and Kinetic Study of Carbon Monoxide Pressure Influence on Rhodium‐Catalyzed Olefin Hydroformylation

The influence of carbon monoxide concentration on the kinetics of the hydroformylation of 3,3‐dimethyl‐1‐butene with a phosphite‐modified rhodium catalyst has been studied for the pressure range p(CO)=0.20–3.83 MPa. Highly resolved time‐dependent concentration profiles of the organometallic intermediates were derived from IR spectroscopic data collected in situ for the entire olefin‐conversion range. The dynamics of the catalyst and organic components are described by enzyme‐type kinetics with competitive and uncompetitive inhibition reactions involving carbon monoxide taken into account. Saturation of the alkyl–rhodium intermediates with carbon monoxide as a cosubstrate occurs between 1.5 and 2 MPa of carbon monoxide pressure, which brings about a convergence of aldehyde regioselectivity. Hydrogenolysis of the acyl intermediate is fast at 30 °C and low pressure of p(CO)=0.2 MPa, but is of minus first order with respect to the solution concentration of carbon monoxide. Resting 18‐electron hydrido and acyl complexes that correspond to early and late rate‐determining states, respectively, coexist as long as the conversion of the substrate is not complete.     

Reaction of the 1,3-phenylenediacetatodicopper(I) pyridine complex with dioxygen,hydrogen peroxide and carbon monoxide

Summary The reactions of 1,3-phenylenediacetatodicopper(I) pyridine, prepared from 1,3-phenylenediacetatocopper(II) by metallic copper, were studied. On oxygenation, a copper-dioxygen complex was formed, whereas carbon monoxide yielded an unstable carbonyl complex. The complexes were characterised by spectroscopic measurements.