天津师范大学 本科毕业论文（设计） 题目：烷基桥联的N-杂环卡宾金属配合物的合成及其结构的 研究 学院：化学学院 学生姓名：方漪芸 学号：08507018 专业：化学 年级：08级 完成日期：2012年05月 指导教师：柳清湘
烷基桥联的氮杂环卡宾金属配合物的合成及其结构的研究 摘要：N-杂环卡宾及其金属配合物在金属配位化学和有机化学中的应用非常广泛，它不仅能与元素周期表中的许多金属元素发生反应并且其得到的金属配合物所显示出来的优良催化活性使其成为最具潜质的催化剂。除此之外，它也开始广泛地应用于精细化工产品的合成中，成为现代有机化学中必不可少的重要物质之一。因此为了使氮杂环卡宾金属配合物的相关合成方法有新的拓展，本文采用烷基桥联的氮杂环卡宾作配体，合成并且得到了一个N-杂环卡宾镍金属配合物的晶体，并对其结构进行了相关研究。 关键词：N-杂环卡宾；金属配合物；合成；结构研究
Synthesis of N-heterocyclic Carbene Metal Complexes by Alkyl Bridge Linkage Abstract：N-heterocyclic carbene and N-heterocyclic carbene mental complexes are widely used in coordination organometallic chemistry and coordination chemistry. Now, it has became one of the hotest topics in the field of chemistry. The study of N-heterocyclic carbine began in 1991, when first free N-heterocyclic carbene was isolated by Ardengo, this has evoked considerable attention. N-heterocyclic carbine always shows high activity, it can react with almost all elements in periodical table.Besides, the excellent catalytic activity of N-heterocyclic carbene mental complexes makes it beco me the most potential catalyst. What’s more, N-heterocyclic carbine have made signficant progesses in the synthesis of fine chemical products,which makes it occupy an important position in organic chemistry. In order to expand the synthesis of N-heterocyclic carbine mental complexes ,we used N-heterocyclic carbine which bridged by alkyl as ligand and one N-heterocyclic carbene nickel complex was prepared. And we have the structure researched.. Key words : N-heterocyclic carbene; metal complex; prepare; structure research
N?Heterocyclic Carbene-Palladium(II)-1-Methylimidazole Complex-Catalyzed Direct C?H Bond Arylation of(Benz)imidazoles with Aryl Chlorides Zheng-Song Gu,?Wen-Xin Chen,?and Li-Xiong Shao*,?,? ?College of Chemistry and Materials Engineering,Wenzhou University,Chashan University Town,Wenzhou,Zhejiang Province 325035,People’s Republic of China ?College of Chemistry and Life Sciences,Zhejiang Normal University,Jinhua,Zhejiang Province321004,People’s Republic of China *Supporting Information INTRODUCTION C2-arylated(benz)imidazoles are frequently found in various pharmaceuticals,biologically active compounds and materials.1 Recently,the transition metal-catalyzed direct C?H bond arylation of(benz)imidazoles has been noticed as a potentially more e?cient and convenient alternative for the straightfor-ward synthesis of such compounds.2However,during the past years,the scope of the arylating reagents is limited to the more active aryl iodides and bromides.3To the best of our knowledge,only very few examples on the palladium-catalyzed direct C2-arylation of(benz)imidazoles using aryl chlorides in the presence of phosphine ligands were reported to date, despite their lower cost and more easy availability.4Therefore, despite that some progress has been made in the direct C2-arylation of(benz)imidazoles,the research for e?cient methods using the more applicable,while less active,aryl chlorides as the arylating reagents is still in great demand.5 Previously,we have reported that a well-de?ned N-heterocyclic carbene-Pd(II)-1-methylimidazole[NHC-Pd(II)-Im]complex 1can easily activate aryl chlorides in traditional C?C couplings such asα-arylation of carbonyl compounds,6Suzuki?Miyaura coupling,7Mizoroki?Heck reaction,8Hiyama reaction9and C?N coupling.10Furthermore,in a very recent communication,we found that NHC-Pd(II)-Im complex1can also e?ciently catalyze the direct C?H bond arylation of(benzo)oxazoles using aryl chlorides as the arylating reagents.11These results thus prompted us to further investigate its application in activating aryl chlorides toward the direct C2-arylation of (benz)imidazoles.Herein,we report these results in detail.■RESULTS AND DISCUSSION Initially,1-methylbenzimidazole2a(0.49mmol)was chosen as the model substrate for the reaction with chlorobenzene3a(2.0equiv)in the presence of NHC-Pd(II)-Im complex1(2.0mol %)under various conditions.For example,in the?rst round, toluene/H2O(2.0mL/0.5equiv)was chosen as the solvents to evaluate the e?ect of bases.The best result was achieved using KO t Bu as the base to give the desired product4a in89%yield (Table1,entry6),while in the presence of other bases such as K2CO3,KOH,K3PO4·3H2O,LiO t Bu and NaO t Bu,almost no product could be detected(Table1,entries1?5).The replacement of solvents from toluene/H2O to THF/H2O and dioxane/H2O resulted in product4a only being isolated in48 and40%yields,respectively(Table1,entries7and8).In addition,in the presence of other solvents such as DMSO/ H2O,DMF/H2O,CH3CN/H2O and DME/H2O,no desired product could be detected(Table1,entries9?12). Furthermore,after careful investigations,it was found that the amount of H2O dramatically a?ected the reaction.That is,the introduction of0.5equiv of H2O was found to be necessary for such transformation.For instance,only18%yield of product4a was obtained when dry toluene was used as the solvent(Table 1,entry13).When1.0equiv of H2O was added,a signi?cantly higher yield(84%)was achieved(Table1,entry14).However, when the amount of H2O was increased to3.0equiv,the yield of4a drastically decreased to5%(Table1,entry15).These results thus encouraged us to further investigate the e?ect of H2O. It is known that KO t Bu will be partially hydrolyzed to KOH and HO t Bu under the above reaction conditions.Therefore, three more control experiments were carried out:(1)the combination of KO t Bu(1.5equiv),KOH(0.5equiv)and HO t Bu(0.5equiv)was introduced instead of KO t Bu(2.0 Received:May9,2014 Published:May28,2014 ?2014American Chemical https://www.doczj.com/doc/0319413456.html,/10.1021/jo5010058|https://www.doczj.com/doc/0319413456.html,.Chem.2014,79,5806?5811
含亚磷酸酯和氮杂环卡宾的混配型镍(Ⅱ)配合物的合成、表征及 其催化性能的研究 本论文设计合成了一系列新的含亚磷酸酯和氮杂环卡宾配体的混配型镍（Ⅱ）配合物,并对它们进行了全面的表征。在此基础上,考察了上述配合物在氯代芳烃、溴代芳烃及苄基氯代烃与联硼酸酯的Miyaura硼化反应中的催化性能。 1、通过二亚磷酸酯二卤化镍Ni[P（OR1） 3]2X2与等摩尔量的氮杂环卡宾配体NHC 的反应合成了含亚磷酸酯和氮杂环卡宾配体的混配型镍（Ⅱ）配合物Ni（NHC）[P（OR1）3]X2{NHC= （R2NH2NH2R2） C,R2=2,4,6-三甲基苯基,SIMes;R2=2,6-二异丙基苯基,SIPr;R2=叔丁基,SItBu;R1=乙基,异丙基;X=溴,氯}1–6和8–10。所有配合物在室温下都是红色（含有SIMes和SIPr）或棕黄色（含有SItBu）固体粉末,对空气不敏感,它们都通过了元 素分析和核磁的表征,其中配合物5、6和9通过了X-ray单晶衍射的表征。 2、考察了混配型镍（Ⅱ）配合物1–6和8–10在氯代芳烃或溴代芳烃与联硼酸酯的Miyaura硼化反应中的催化性能,发现这些配合物具有明显的亚磷酸酯配体和氮杂环卡宾配体之间的协同效应,并且亚磷酸酯配体和氮杂环卡宾配体结构的改变对配合物的催化性能有很大影响。其中,配合物1在氯代芳烃与联硼酸新戊二醇酯（B2nep2）的Miyaura硼化反应中表现出最优的催化活性,而配合物2在溴代芳烃与联硼酸频哪醇酯 （B2pin2）的Miyaura硼化反应中的催化效果最佳。
本科毕业论文（设计） 题目：烷基桥联的N-杂环卡宾金属配合物的合成及其结构的研究
烷基桥联的氮杂环卡宾金属配合物的合成及其结构的研究 摘要：N-杂环卡宾及其金属配合物在金属配位化学和有机化学中的应用非常广泛，它不仅能与元素周期表中的许多金属元素发生反应并且其得到的金属配合物所显示出来的优良催化活性使其成为最具潜质的催化剂。除此之外，它也开始广泛地应用于精细化工产品的合成中，成为现代有机化学中必不可少的重要物质之一。因此为了使氮杂环卡宾金属配合物的相关合成方法有新的拓展，本文采用烷基桥联的氮杂环卡宾作配体，合成并且得到了一个N-杂环卡宾镍金属配合物的晶体，并对其结构进行了相关研究。 关键词：N-杂环卡宾；金属配合物；合成；结构研究
Synthesis of N-heterocyclic Carbene Metal Complexes by Alkyl Bridge Linkage Abstract：N-heterocyclic carbene and N-heterocyclic carbene mental complexes are widely used in coordination organometallic chemistry and coordination chemistry. Now, it has became one of the hotest topics in the field of chemistry. The study of N-heterocyclic carbine began in 1991, when first free N-heterocyclic carbene was isolated by Ardengo, this has evoked considerable attention. N-heterocyclic carbine always shows high activity, it can react with almost all elements in periodical table.Besides, the excellent catalytic activity of N-heterocyclic carbene mental complexes makes it beco me the most potential catalyst. What’s more, N-heterocyclic carbine have made signficant progesses in the synthesis of fine chemical products,which makes it occupy an important position in organic chemistry. In order to expand the synthesis of N-heterocyclic carbine mental complexes ,we used N-heterocyclic carbine which bridged by alkyl as ligand and one N-heterocyclic carbene nickel complex was prepared. And we have the structure researched.. Key words :N-heterocyclic carbene; metal complex; prepare; structure research
(19)中华人民共和国国家知识产权局 (12)发明专利申请 (10)申请公布号 (43)申请公布日 (21)申请号 201910154963.X (22)申请日 2019.03.01 (71)申请人 山西师范大学 地址 041000 山西省临汾市尧都区贡院街1 号 (72)发明人 杨俊娟 王君文 吴元元 王昕 (74)专利代理机构 北京中索知识产权代理有限 公司 11640 代理人 刘翔 (51)Int.Cl. B01J 31/28(2006.01) C07C 1/32(2006.01) C07C 15/14(2006.01) C07C 41/30(2006.01) C07C 43/205(2006.01) C07C 201/12(2006.01)C07C 205/06(2006.01)C07C 17/263(2006.01)C07C 25/18(2006.01)C07C 205/12(2006.01) (54)发明名称一种氮杂环卡宾共价有机框架材料负载钯的催化剂制备及应用(57)摘要一种氮杂环卡宾共价有机框架材料负载钯的催化剂制备方法以及基于该催化剂的碳-碳偶联反应的催化应用。非均相催化剂的合成步骤为：以含氮杂环卡宾的共价有机框架材料为载体(COF -NHC)，负载金属钯即得碳-碳偶联反应的催化剂(Pd@COF -NHC)。该反应以卤代芳烃和芳基苯硼酸为原料，以碳酸钾为碱，在水溶剂中室温下反应1.0h即得目标产物，收率均在90％以上。以溴苯和苯硼酸为反应模板，所制得的催化剂在循环使用十次后，收率依然可达97％。本发明的金属钯非均相催化剂具有用量小，结构稳定，活性高，可多次循环使用的特点，具有很好的工业化 应用前景。权利要求书2页 说明书7页 附图3页CN 109894153 A 2019.06.18 C N 109894153 A
毕业论文文献综述 应用化学 N-杂环卡宾的合成和应用 1 前言 1.1 卡宾 卡宾（carbene）又称碳烯，一般以R2C表示，指碳原子上只有两个键连有基团，还剩有两个未成键电子的高活性中间体。卡宾的寿命远低于一秒，只能在低温下（77K以下）捕获，在晶格中加以分离和观察。卡宾与碳自由基一样，属于不带正负电荷的中性活泼中间体。卡宾只有6个价电子，含有一个电中性的二价碳原子，在这个碳原子上有两个未成键的电子。卡宾是一种强Lewis酸，具有很强的亲电性。 1.2 N-杂环卡宾 最早对N-杂环卡宾的研究起始于1960年，当时Wanzlick[1]等对噻唑-2-碳烯进行了详尽透彻的研究。由于噻唑-2-碳烯类化合物异常的活泼性，尽管在当时Wanzlick并没有成功通过分离技术得到N-杂环卡宾，但是他们意识到咪唑环中邻位氮原子的给电子效应可以稳定2-位上的卡宾中心，这一思想为之后的N-杂环卡宾化学的发展奠定了基础。在这之后，N-杂环卡宾引起了化学家们的广泛的研究兴趣。在近十几年来，N-杂环卡宾的的研究得到了迅速的发展，特别是在金属成键的配位化学这一领域。最近几年，N-杂环卡宾的金属络合物作为一种催化剂，已经在多个领域取得了广泛的应用。 N-杂环卡宾被看作是一种有机膦配体的代替品。在某一些有机金属催化反应方面，N-杂环卡宾被当做配体已经成功取代了应用广泛的膦配体。由于在催化方面的出色表现，N-杂环卡宾配合物的合成及其催化性质的研究受到了国内外化学家的关注。 1.2.1N-杂环卡宾的分类及其应用 常见的N-杂环卡宾根据环上氮原子的数目不同或氮原子位置的不同有咪唑型卡宾，三唑型卡宾等。N-杂环卡宾一般以单线态形式存在，卡宾碳原子采用sp2杂化形式，卡宾碳原子周围有6个电子，是一个缺电子体系，卡宾碳原子上的一对电子处在σ轨道上。从电子共轭效应考虑，2个氮原子p轨道上的孤对电子和卡宾碳原子上的空p轨道可以发生给电子共轭效应，这样降低了卡宾碳原子的缺电子性。从电子诱导效应考虑，2个
2010年，Michael G. Gardiner 和他的同事合成了新型的氮杂环卡宾化合物，A colorless solution of 1 over anhydrous Na2CO3 in dry MeOH was heated at 508C for two hours to give a red solution, from which red crystals of 2 were obtained in 84% yield after filtration and concentration (Scheme 1).[8] Complex 2 has high stability as a solid (more than one year) and in MeOH and THF (several months). The complex is tolerant to moisture, but reacts quickly with atmospheric oxygen in solution and the solid state. Peter D. W. Boyd, Alison J. Edwards, Michael G. Gardiner, Angew. Chem. Int. Ed. 2010, 49, 6315 –6318. 2008年，Takeshi Makino和他的同事得到了具有二齿氮杂环配体的钯配合物，The bidentate NHC-palladium complexes 4a–e were prepared by the reaction of 1-(4-iodoaryl)-3-aryl-4,5-dihydroimidazolinium salt (1)[16] and xanthenediboronic acid (2)[17] in the presence of Pd(PPh3)4 and Ag2O followed by palladation[18] (Scheme 1). The bis(imidazolidene) derivative 6 was also synthesized in a similar way (Scheme 2).