發(fā)布時(shí)間：2018-01-05 07:42

  本文關(guān)鍵詞：三甲基膦支持的鈷配合物對(duì)醛基C-H鍵和Si-H鍵活化的探究以及催化性質(zhì)的探索　出處：《山東大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 三甲基膦 鈷 碳?xì)滏I活化 硅氫鍵活化 硅氫化還原

【摘要】：有機(jī)膦配體對(duì)于過(guò)渡金屬配合物有著非常強(qiáng)的穩(wěn)定作用。在金屬有機(jī)化學(xué)中,人們通常通過(guò)改變膦配體的性質(zhì)來(lái)調(diào)節(jié)金屬配合物的電子密度,從而改變配合物的性質(zhì)。三甲基膦作為一種膦配體,具有體積小、配位性強(qiáng)、光譜信號(hào)易識(shí)別等優(yōu)點(diǎn),從而常被應(yīng)用于金屬有機(jī)配合物的構(gòu)建。碳?xì)滏I廣泛地存在于有機(jī)物中。在一定條件下切斷碳?xì)滏I并將其定向地轉(zhuǎn)化為其他基團(tuán)可以提高有機(jī)合成過(guò)程中的高效性和原子經(jīng)濟(jì)性,有效簡(jiǎn)化和縮短反應(yīng)步驟。與傳統(tǒng)方法相比,過(guò)渡金屬化合物在這方面具有獨(dú)特的應(yīng)用潛力。醛基中的碳?xì)滏I較為活潑,不但容易與過(guò)渡金屬化合物發(fā)生反應(yīng)從而實(shí)現(xiàn)碳?xì)滏I的活化,還有可能發(fā)生進(jìn)一步的脫羰反應(yīng)。α,β不飽和醛是一種特殊的醛,由于其結(jié)構(gòu)中共軛的碳碳雙鍵和碳氧雙鍵都可以被活化,其與過(guò)渡金屬化合物的反應(yīng)產(chǎn)物會(huì)具有一些獨(dú)特的性質(zhì)。目前關(guān)于這方面的研究主要集中在釕、銠、鉬、銥等貴金屬,而對(duì)于廉價(jià)金屬鈷的研究較少。其低廉的價(jià)格、獨(dú)特的性質(zhì)以及環(huán)境友好的特性在有機(jī)合成應(yīng)用中非常有潛力。近年來(lái),硅基過(guò)渡金屬配合物也吸引越來(lái)越多研究者的目光,而通過(guò)過(guò)渡金屬配合物活化硅氫鍵從而發(fā)生氧化加成反應(yīng)是制備此類化合物的重要方法之一。通過(guò)對(duì)硅基金屬配合物的研究可以幫助人們更加深刻理解過(guò)渡金屬參與的催化反應(yīng)的機(jī)理。其中,利用NSiN型的硅氮烷配體與過(guò)渡金屬配合物反應(yīng)來(lái)合成此類化合物是一種新的合成途徑,且硅氮烷本身更是在材料化學(xué)、有機(jī)合成等領(lǐng)域展現(xiàn)出廣闊的應(yīng)用前景。本論文主要分為以下三個(gè)部分:第一部分利用三甲基膦支持的CoMe(PMe3)4,CoCl(PMe3)3和Co(PMe3)4與三種肉桂醛的衍生物反應(yīng),得到三種η4型的鈷化合物1-3和五種η2型的鈷化合物4-8�；衔�1-8的結(jié)構(gòu)經(jīng)過(guò)IR和NMR的完整表征,其中化合物1-4和8的結(jié)構(gòu)進(jìn)一步通過(guò)單晶X射線衍射分析證實(shí)。第二部分利用三甲基膦支持的CoCl(PMe3)3和CoMe(PMe3)4分別與兩種硅氮烷發(fā)生反應(yīng),得到了兩種硅氮烷配位的鈷化合物9-10�；衔�10的結(jié)構(gòu)經(jīng)過(guò)IR和NMR的表征,且進(jìn)一步通過(guò)單晶X射線衍射分析證實(shí)。第三部分以化合物10做催化劑以三乙氧基硅烷作為氫源催化醛酮的硅氫化反應(yīng),但是該反應(yīng)對(duì)于底物的適用性較差,有待進(jìn)一步的改進(jìn)。
[Abstract]:Organic phosphine ligands are very stable to transition metal complexes. In organometallic chemistry, the electron density of metal complexes is regulated by changing the properties of phosphine ligands. As a phosphine ligand, trimethyl phosphine has the advantages of small volume, strong coordination, easy recognition of spectral signals, and so on. Thus it is often used in the construction of organometallic complexes. Hydrocarbon bonds are widely present in organic compounds. Cutting off the hydrocarbon bonds and converting them to other groups can improve the efficiency of organic synthesis under certain conditions. Sex and atomic economics. Effective simplification and shortening of reaction steps. Transition metal compounds have unique potential applications in this area compared with traditional methods. Carbo-hydrogen bonds in the aldehyde group are active. It is not only easy to react with transition metal compounds to realize the activation of hydrocarbon bond, but also possible to decarbonylation further. 偽, 尾 unsaturated aldehydes are special aldehydes. Because the conjugated carbon-carbon double bonds and carbon-oxygen double bonds in their structures can be activated, the products of their reactions with transition metal compounds will have some unique properties. At present, the research on this aspect is mainly focused on ruthenium and rhodium. Molybdenum, iridium and other precious metals, but less research on low-cost cobalt. Its low price, unique properties and environmentally friendly properties in organic synthesis has great potential in recent years. Silicon-based transition metal complexes have attracted more and more researchers' attention. It is one of the important methods to prepare the transition metal complexes by activating the hydrosilyl bond through the transition metal complexes. The study of the silicon-based metal complexes can help people to understand the transition metals more deeply. Participate in the mechanism of catalytic reaction. It is a new way to synthesize NSiN type silane ligand and transition metal complex, and silane itself is in the material chemistry. Organic synthesis and other fields show broad application prospects. This paper is divided into the following three parts: the first part is CoMe(PMe3)4 supported by trimethyl phosphine. CoCl(PMe3)3 and Co(PMe3)4 reacted with three derivatives of cinnamaldehyde. Three kinds of 畏 4 cobalt compounds 1-3 and five 畏 2 cobalt compounds 4-8 were obtained. The structures of compounds 1-8 were characterized by IR and NMR. The structures of compounds 1-4 and 8 were further confirmed by single crystal X-ray diffraction. In the second part, CoCl(PMe3)3 and CoMePMe3 supported by trimethyl phosphine were used. 4reacted with two kinds of silane respectively. Two kinds of cobalt compounds coordinated with silane were obtained. The structure of compound 10 was characterized by IR and NMR. The third part uses compound 10 as catalyst to catalyze the hydrosilylation of aldehydes and ketones with triethoxy silane as the hydrogen source, but this reaction is not suitable for the substrate. Further improvements are needed.
【學(xué)位授予單位】：山東大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.4;O643.36

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本文編號(hào)：1382219