本文選題：C-C鍵活化 + 過渡金屬�。� 參考：《東北師范大學》2016年碩士論文

【摘要】：碳-碳(C-C)鍵的斷裂是有機化學的基礎問題,過渡金屬催化C-C鍵活化是有效途徑之一。其中科研工作者們發(fā)展了一系列的催化碳-碳鍵官能團化的反應體系,如釕、銠、鈀、鐵、鉆、鎳、銥、鎢、錸、鋨和金等過渡金屬配合物。這些過渡金屬配合物能夠高效的催化不飽和烴(炔烴或烯烴)插入C-C鍵,從而實現(xiàn)官能團的轉(zhuǎn)化或者擴環(huán)反應。新穎的協(xié)同催化策略包括有機-有機,金屬-金屬和有機-金屬協(xié)同作用已經(jīng)引起了人們的重視。而且,在C-C鍵活化領域,路易斯酸(LA)和過渡金屬化合物結(jié)合有望成為一種高效有力的手段。在實驗中,催化劑的設計與優(yōu)化往往需要大量試驗。通過計算機程序模擬催化過程是認識催化機理的重要手段。當掌握催化劑在催化反應中的作用機理時,通過比較不同催化劑對反應的影響,進而改善、設計新型催化劑。過渡金屬催化機理的理論研究是目前催化劑設計與合成的重要指導支持。本論文首先采用密度泛函方法(DFT)詳細探討了過渡金屬催化不飽和烴插入C-C鍵的反應機制,并與實驗結(jié)果對照,為實驗設計更為高效的催化劑提供理論依據(jù)。本文的研究結(jié)果如下：1.鎳/路易斯酸協(xié)同催化炔烴選擇性插入2,3,5,6-四氟苯甲腈C-CN鍵反應機制的理論研究。本文詳細研究了零價Ni/BPh_3協(xié)同催化的2-丁炔插入2,3,5,6-四氟苯甲腈的反應機制。結(jié)果表明,此反應完整的催化循環(huán)包括Ni遷移,氧化加成,炔烴插入和還原消除。其中炔烴插入(ΔG°(?)=21.9kcal/mol)是決速步驟。通過對比有無助催化劑BPh_3參與的反應勢能面表明,BPh_3的參與能夠有效降低Ni遷移,氧化加成以及炔烴插入步驟的活化能壘,特別是Ni遷移步驟的反應能壘降低了3.4 kcal/mol,計算結(jié)果與實驗事實一致。此外,本文成功解釋了Ni0催化劑選擇性活化C-CN鍵的原因,并預測單膦配體催化劑Ni(PPh_3)(AL)對此反應體系具有更好的催化活性,活化能AG°(?)=10.0 kcal/mol(炔烴插入),為實驗合成提供了新的方向。2.鎳催化1,3-二烯和3-氮雜環(huán)丁酮環(huán)加成反應機制的理論研究。本文利用DFT方法詳細探討了鎳催化1-Boc-3-氮雜環(huán)丁酮和1,3-二烯的環(huán)加成反應的β-碳消除和氧化加成兩種可能反應機制。結(jié)果表明,通過β-碳消除斷裂C-C鍵的能壘高達48.0 kcal/mol,說明此反應機制并非經(jīng)過傳統(tǒng)的β-碳消除。氧化加成機制由氧化加成,烯烴插入和還原消除三個基元步驟組成,而且烯烴插入是決速步驟(AG°(?)=32.2 kcal/mol)。這表明這個反應是經(jīng)過氧化加成的反應機制進行的。這有助于我們更好的理解此類反應的機制,從而為實驗上設計更為高效的催化劑,有效的降低決速步驟的活化能提供理論依據(jù)。
[Abstract]:The fracture of C-C bond is a fundamental problem in organic chemistry, and the activation of C-C bond catalyzed by transition metal is one of the effective ways. Among them, researchers have developed a series of transition metal complexes such as ruthenium, rhodium, palladium, iron, drill, nickel, iridium, tungsten, rhenium, osmium and gold. These transition metal complexes can efficiently catalyze unsaturated hydrocarbons (alkynes or alkenes) into C-C bonds to achieve functional group conversion or ring expansion reaction. Novel synergistic catalysis strategies, including organic-organic, metal-metal and organic-metal synergistic effects, have attracted much attention. Furthermore, in the field of C-C bond activation, the binding of Lewis acid and transition metal compounds is expected to be an efficient and powerful means. In experiments, the design and optimization of catalysts often require a large number of tests. The simulation of catalytic process by computer program is an important means to understand the mechanism of catalysis. The new catalyst was designed by comparing the influence of different catalysts on the reaction and improving the mechanism of catalyst in the catalytic reaction. The theoretical study on the catalytic mechanism of transition metals is an important support for the design and synthesis of catalysts. In this paper, the mechanism of transition metal-catalyzed unsaturated hydrocarbon insertion into C-C bond is discussed in detail by using density functional method (DFT), and compared with the experimental results, it provides a theoretical basis for the design of more efficient catalysts. The results of this paper are as follows: 1: 1. A theoretical study on the Mechanism of selective insertion of alkynes by Nickel / Lewis Acid in the C-CN Bond reaction of Tetrafluorobenzonitrile (Tetrafluorobenzonitrile). In this paper, the mechanism of 2-butadiene-2-butadiene-6-tetrafluorobenzonitrile catalyzed by zero-valent Ni/BPh_3 has been studied in detail. The results show that the complete catalytic cycle includes Ni migration, oxidation addition, alkynes insertion and reduction elimination. The insertion of alkynes (螖 G 擄) is a critical step. By comparing the potential energy surface of the reaction with or without the co-catalyst BPh_3, it is shown that the participation of BPhS _ 3 can effectively reduce the activation energy barrier of Ni migration, oxidation addition and alkynes insertion steps. In particular, the reaction barrier of Ni transport step decreases by 3.4 kcal / mol, and the calculated results are in agreement with the experimental results. In addition, the reason for the selective activation of C-CN bond over Ni0 catalyst was successfully explained, and it was predicted that the single phosphine ligand nip PPh3AL had better catalytic activity for this reaction system. The activation energy AG 擄C / L was 10.0 kcal / mol (alkynes insertion), which provided a new direction for the experimental synthesis. A theoretical study on the mechanism of cycloaddition reaction of 1: 3-diene and 3-azacyclic butanone catalyzed by nickel. In this paper, the mechanism of 尾 -carbon elimination and oxidative addition of 1-Boc-3-azacyclobutanone and 1-oc-3-diene catalyzed by nickel was discussed in detail by DFT method. The results show that the barrier of C-C bond cleavage by 尾 -carbon is up to 48.0 kcal / mol, which indicates that this reaction mechanism is not eliminated by traditional 尾 -carbon elimination. The oxidation addition mechanism consists of three basic steps: oxidation addition, olefins insertion and reduction elimination, and olefin insertion is a critical step, which is 32.2 kcal / mol ~ (-1) 路mol ~ (-1). This indicates that the reaction is carried out by the mechanism of oxidation addition. This will help us to better understand the mechanism of such reactions, thus providing a theoretical basis for the experimental design of more efficient catalysts and the effective reduction of the activation energy of the critical step.
【學位授予單位】：東北師范大學
【學位級別】：碩士
【學位授予年份】：2016
【分類號】：O621.251

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