随着工业生产活动的增多，产生大量温室气体，引起了一系列环境问题。因此将CO₂转化为高附加值化学品引起了广泛关注，其中CO₂转化为环状碳酸酯是一种原子经济100%的方法。并且由于CO₂是惰性气体，CO₂的转化需要高温、高压的严苛条件。本文设计了一类Zn配合物用于催化CO₂偶联反应、N-杂环类化合物脱氢反应。

1．针对常用于环氧化物和CO₂环加成反应的Zn金属催化剂存在着配体不稳定、合成过程复杂、无水、无氧的苛刻条件和产率较低的问题。在课题组配体合成的基础上，合成了[NN]-型Zn配合物。该配合物的合成步骤简单，在空气氛围中能够快速合成，通过过滤、干燥即可得到纯净的化合物。

2．将配合物应用在CO₂和环氧化物的偶联反应时，能够在常温、常压，较低的催化剂和季铵盐负载量的条件下催化末端环氧化物生成环状碳酸酯，适当的升高温度和压力也同样适用于内部环氧化物和植物油基环氧化物底物。通过控制实验、高分辨质谱研究发现，将催化剂、TBAI和环氧化物三者反应时，发现了催化剂和环氧化物配位的中间体，因此，提出了催化剂和TBAI发生阴离子交换后的产物是真正起催化作用的活性物质。

3．随后将[NN]-型Zn配合物应用到CO₂和丙炔胺的环加成反应，成功制备了一系列噁唑烷酮化合物。底物普适性研究得出，苄基取代基底物表现出中等偏上的产率，而高位阻底物在升高温度后也可获得中等产率。在机理探究实验中，采用红外谱图、高分辨质谱来探究机理，发现Zn配合物主要起到活化丙炔胺的炔基氢的作用。

4．为了拓展[NN]-型Zn配合物应用性，选择将其应用到N-杂环类化合物（吲哚啉和1,2,3,4-四氢喹啉）的脱氢反应中，常用的脱氢催化剂是Ir、Ru、Pd等催化剂，但上述催化剂均属于贵金属催化剂。本文以Zn配合物为催化剂，叔丁基过氧化氢为氧化剂，在温度110 ^oC下反应24 h，生成相应的不饱和脱氢产物，并探究了一系列不同取代基底物的反应效果。通过控制实验确定化合物的脱氢位点，高分辨质谱监测反应过程的中间体，推测出Zn配合物催化N-杂环类化合物脱氢的反应机理。

With the increase of industrial production activities, a large amount of greenhouse gases are generated, causing a series of environmental problems. Therefore, the conversion of CO₂ into chemicals with high added value has attracted wide attention, and the conversion of CO₂ into cyclic carbonate is a 100% atom economy method. And since CO₂ is an inert gas, its conversion requires harsh conditions of high temperature and pressure. In this paper, a class of Zn complexes were designed to catalyze CO₂ coupling reaction and dehydrogenation of N-heterocyclic compounds.

1. The Zn metal catalyst commonly used in epoxide and CO₂ cycloaddition reaction has the problems of unstable ligand, complex synthesis process, anhydrous and oxygen free harsh conditions and low yield. On the basis of ligand synthesis in the research group, [NN] - type Zn complexes were synthesized. The synthesis steps of this complex are simple and can be quickly synthesized in an air atmosphere. Pure compounds can be obtained by filtration and drying.

2. When the complex is applied to the coupling reaction of CO₂ and epoxides, it can catalyze the end epoxides to generate cyclic carbonate under the conditions of normal temperature, normal pressure, low catalyst and quaternary ammonium salt loading. Appropriate temperature and pressure rise are also applicable to the internal epoxides and vegetable oil-based epoxides substrates. Through controlled experiments and high-resolution mass spectrometry studies, it was found that when the catalyst, TBAI, and epoxide were reacted, intermediates were found to coordinate between the catalyst and epoxide. Therefore, it was proposed that the product of anion exchange between the catalyst and TBAI is the active substance that truly plays a catalytic role.

3. Subsequently, [NN] - type Zn complexes were applied to the cycloaddition reaction of CO₂ and propionamide, and a series of oxazolidinones were successfully prepared. Studies on the universality of substrates have shown that benzyl substituted substrates exhibit moderate to high yields, while high-order hindered substrates can also achieve moderate yields at elevated temperatures. In the mechanism exploration experiment, infrared spectroscopy and high-resolution mass spectrometry were used to explore the mechanism, and it was found that Zn complexes can mainly activate the acetyl hydrogen of propargylamine.

4. In order to expand the application of [NN] - type Zn complex, it is selected to be applied to the dehydrogenation of N-heterocyclic compounds (indoline and 1,2,3,4-tetrahydroquinoline). The commonly used dehydrogenation catalysts are Ir, Ru, Pd and other catalysts, but the above catalysts are noble metal catalysts. This article uses Zn complex as catalyst and tert butyl hydrogen peroxide as oxidant to react at 110 ° C for 24 h to generate corresponding unsaturated dehydrogenation products, and explores the reaction effects of a series of different substituted substrates. By controlling experiments to determine the dehydrogenation sites of compounds and monitoring the intermediates in the reaction process using high-resolution mass spectrometry, the reaction mechanism of Zn complexes catalyzing the dehydrogenation of N-heterocyclic compounds is inferred.

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