三甲基膦支持的铁、钴和镍希夫碱配合物的合成及性质研究

发布时间：2018-05-07 15:38

本文选题：C-H键活化 + Fe、Co和Ni　；参考：《山东大学》2017年硕士论文

【摘要】：C-H键活化作为有机化学的"圣杯",备受化学家的青睐。C-H键活化的目标是将键能较高的惰性C-H键转化成键能较低的键,从而合成出目标物质。这是各种有机合成反应和催化反应的关键性步骤,对于有机合成化学尤其是天然产物和药物的合成具有十分重要的意义。有机化合物结构上的各种修饰以及各类化学反应,归根结底都是对C-H键的活化和功能化。过渡金属能够在十分温和的条件一下活化C-H键,并且得到的有机金属配合物在有机合成以及催化反应方面具有十分重要的意义。因此过渡金属参与的C-H键活化成为实现C-H键活化最为有效的手段和途径。起初的探索都是集中在Ru、Rh、Pd、lr、Pt和Os等贵金属上,但是它们价格昂贵,并且毒性大,违背了可持续发展观和绿色化学的理念。因此,利用储量丰富,廉价易得,毒性低,污染少的Fe、Co和Ni等廉价金属代替贵金属来实现C-H键的活化是非常有现实意义的。PMe3作为一种支持配体具有体积小,配位能力强以及光谱特性易于表征等优点,广泛的应用在科研探索中。本论文主要分为以下三部分内容:1.三甲基膦支持的Fe、Co和Ni配合物对苄胺希夫碱体系中的C-H键活化及相关性质研究。CoMe(PMe_3)_4和Fe(PMe_3)_4与苄胺希夫碱配体L1-L3反应,活化了苄基上的C(sp3)-H键,得到2-氮杂烯丙基钴和铁配合物1-3和8-10。CoMe(PMe_3)_4同样可以实现甲胺希夫碱L4中的C(sp3)-H键的活化,得到2-氮杂烯丙基钴配合物4。而Co(PMe_3)_4并未实现L1中的C-H键活化,得到的是简单的π配位的零价钴配合物7。CoCl(PMe3)3和Ni(PMe_3)_4与L1的反应并未得到可以表征的结果。2-氮杂烯丙基钴配合物1与碘甲烷反应,通过氧化加成和C-N偶联得到离子型的钴配合物5;1与CO反应得到含有两个羰基配位的钴钴配合物6。2-氮杂烯丙基铁配合物8与溴乙烷通过单电子氧化加成得到配合物11;8 与 CO反应得到羰基铁配合物12。2.三甲基膦支持的Fe、Co和Ni配合物对萘胺希夫碱体系中的C-H键活化及相关性质研究。CoMe(PMe_3)_4与萘胺希夫碱配体L5反应,活化了醛基上的C(sp2)-H键,得到萘胺钴配合物13。但是Co(PMe_3)_4和Fe(PMe_3)_4与L5反应都未能实现C-H键的活化,得到的均是简单的π配位萘胺钴配合物16和萘胺铁配合物17。同时CoCl(PMe3)3和Ni(PMe_3)_4与L5的反应并未得到可以表征的结果。钴配合物13与碘甲烷反应,通过单电子氧化加成得到钴碘配合物14;13与CO反应得到含有两个羰基配位的配合物15。配合物17与CO反应得到羰基铁配合物18。3.三甲基膦支持的Fe、Co和Ni配合物对苯胺希夫碱体系中的C-H键活化及相关性质研究。CoMe(PMe_3)_4与萘胺希夫碱配体L6反应,活化了醛基上的C(sp2)-H键,得到苯胺钴配合物19。但是Co(PMe_3)_4与L6反应则未能实现C-H键的活化,得到的是简单的π配位苯胺钴配合物20。Fe(PMe_3)_4与L6反应,活化了醛基和苯环上两个C(sp2)-H键,得到苯胺铁配合物21,配合物21中的一个PMe3很容易与N2发生取代反应,得到N2配位的铁配合物22。同时CoCl(PMe3)3和Ni(PMe_3)_4与L6的反应并未得到可以表征的产物。配合物21和22的混合物与CO反应,得到单一的羰基配位的铁配合物23。论文中的所有金属配合物都得到了完整的光谱表征,并且有多个配合物的结构得到了单晶X-Ray衍射的进一步证实。
[Abstract]:C-H bond activation as the "Holy Grail" of organic chemistry, the goal of chemists' favor of.C-H bond activation is to convert a higher inert C-H bond into a lower bond to synthesize a target substance. This is a key step in various organic synthesis reactions and catalytic reactions, and to organic synthetic chemistry, especially natural products and drugs. Synthesis is of great significance. The various modifications on the structure of organic compounds and various chemical reactions are, in the final analysis, the activation and functionalization of the C-H bond. The transition metal can activate the C-H bond at very mild conditions, and the obtained organic metal complexes are very heavy in the presence of mechanical synthesis and catalytic reactions. Therefore, the C-H bond activation involved in transition metals is the most effective means and way to achieve the activation of C-H bonds. The initial exploration is concentrated on precious metals such as Ru, Rh, Pd, LR, Pt and Os, but they are expensive and toxic and violate the concept of sustainable development and green chemistry. Therefore, rich and cheap reserves are used. Easy to obtain, low toxicity, low pollution of Fe, Co and Ni and other cheap metals instead of precious metals to realize the activation of C-H bonds is a very realistic.PMe3 as a supporting ligand with small volume, strong coordination ability and easy to characterize the spectral characteristics. It is widely used in research and exploration. This paper is divided into three parts: 1. Three methyl phosphine supported Fe, Co and Ni complexes for the C-H bond activation and related properties of benzylamine Schiff base system;.CoMe (PMe_3) _4 and Fe (PMe_3) _4 and benzylamine Schiff base ligand L1-L3 reaction, activation of the benzyl radical bond, obtained the aza allyl cobalt and iron complexes 1-3, and also can realize methylamine Schiff alkali The activation of C (SP3) -H bond in 4 obtained 2- nitrogen heteropropyl cobalt complex 4. and Co (PMe_3) _4 did not activate C-H bond in L1. The addition and C-N coupling obtained the ionic cobalt complex 5; 1 and the CO reaction obtained the cobalt cobalt complex containing two carbonyl complexes, 6.2- heteroallyl iron complex 8 and bromo ethane obtained by the addition of single electron oxidation to obtain the complex 11; 8 and CO reaction to the carbonyl iron complex 12.2. three methyl phosphine supported Fe, Co and Ni complexes to naphthalene Schiff C-H bond activation and related properties in the alkali system study.CoMe (PMe_3) _4 reaction with naphthalene Schiff base ligand L5, activated the C (SP2) -H bond on the aldehyde group, and obtained the naphthalene cobalt complex 13., but both Co (PMe_3) _4 and Fe reaction failed to realize the activation of the bond bond, and the simple coordination of the complex naphthalene cobalt complex 16 and naphthalene iron was obtained. The reaction of substance 17. and CoCl (PMe3) 3 and Ni (PMe_3) _4 and L5 did not be characterized. Cobalt complex 13 reacted with iodized methane and obtained cobalt iodine complex 14 by addition of single electron oxidation; 13 and CO reaction obtained two carbonyl coordination complexes 17 with CO, which were supported by the carbonyl iron complex, 18.3. three methyl phosphine. Fe, Co and Ni complexes have a study on the C-H bond activation and related properties of aniline Schiff base system. The reaction of.CoMe (PMe_3) _4 with the naphthalene Schiff base ligand L6, activated the C (SP2) -H bond on the aldehyde group, and obtained aniline cobalt complex 19., but the activation of the bond was not realized by Co. The reaction of E (PMe_3) _4 with L6 activates two C (SP2) -H bonds on the aldehyde group and the benzene ring, and obtains the aniline iron complex 21. One of the PMe3 in the complex 21 is easily substituted with N2, and the reaction of the iron complex of the N2 coordination is 22. and the reaction of CoCl (PMe3) 3 and the reaction is not characterized. All the metal complexes in the single carbonyl coordination compound 23. obtained the complete spectral characterization, and the structure of multiple complexes has been further confirmed by the single crystal X-Ray diffraction.

【学位授予单位】：山东大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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