论文总字数：20964字

摘 要

亚铜簇合物因为其结构的多样性，反应环境温和等特性吸引了众多科学家的关注，国内外科学家对亚铜簇合物在热催化和可见光催化方面进行了大量研究。近年来，人们发现亚铜簇合物对乌尔曼型C-X偶联反应有着较为高效的催化活性。

由于亚铜簇合物簇中心的几何多样性等原因，使得亚铜簇合物拥有新颖多样的结构单元，各种多维构型，优良的光学性能和催化性能。根据软硬酸碱理论中的“软软相配”原则，属于软碱的Se,Te和软酸的Cu(I)可以合成稳定的碲醚硒醚亚铜簇合物，同时引入结构稳定且对光催化有促进作用的二茂铁基团，形成稳定且催化活性较好的簇合物，期待能得到优异的催化体系。

本论文设计了合成两种二茂铁碲醚配体L1,L2,及其对应的二茂铁碲醚亚铜簇合物1，2，研究了其单晶结构并进行了表征。同时基于亚铜簇合物的光活性，我们研究了簇合物1和2在可见光区400-650nm处，亚铜簇合物1有着较高的吸收，在400-550nm处亚铜簇合物2有着较高的吸收。因此，我们选择蓝色 LED（459nm）作为激发光源。最终发现亚铜簇合物1的催化活性更好。最终产率达到59%。最后探讨了相关的光催化性质，和对光催化性能进行改进。同时因为亚铜簇合物光催化的洁净，安全，绿色，对绿色化学的应用也有一定的理解分析。

关键词：碲醚 亚铜簇合物 光催化 C-C偶联 机理

Synthesis and Photocatalytic C-C Coupling of Ferrocenyltelluroethers Copper(I) Halide Clusters

Abstract

Because of its structural diversity and mild reaction environment, cuprous clusters have attracted the attention of many scientists. Domestic and foreign scientists have done a lot of research on the thermal catalysis and visible light catalysis of cuprous clusters. In recent years, it has been found that cuprous clusters have a relatively high catalytic activity for the Ullmann C-X coupling reaction.

Due to the geometrical diversity of the center of the cuprous clusters, the cuprous clusters have novel and diverse structural units, various multi-dimensional configurations, excellent optical properties and catalytic properties. According to the principle of “soft and soft matching” in the theory of soft and hard acid and alkali, Cu(I), which is a soft base, Se, Te which are soft acid, can synthesize a stable bismuth ether selenoether cuprous cluster. At the same time introduce structural stability and the photocatalytic ferrocene group promotes the formation of a stable and catalytically active cluster, and it is expected that an excellent catalytic system can be obtained.

In this thesis, two kinds of ferrocenium ether ligands L1, L2 and their corresponding copper (I) cluster which based on ferrocenyltelluroethers ligands, were synthesized. The single crystal structure was characterized.And based on the photoactivity of cuprous clusters, we studied clusters 1 and 2. At 400-650 nm in the visible region ,cuprous cluster 1 has a higher absorption, and at 400-550 nmcuprous clusters 2 has a high absorption. Therefore, we chose blue LED (459nm) as the excitation source. It was finally found that the cuprous cluster 1 has a better catalytic activity. The final yield reached 59%. Finally, the related photocatalytic properties and the improvement of photocatalytic performance are discussed. At the same time, because the cuprous clusters are photocatalytic clean, safe, green, and have a certain understanding of the application of green chemistry.

KEYWORDS: Telluroethers, Copper(I) cluster, Photocatalysis, C-C coupling , Mechanism

目 录

摘要....................................................................................................Ⅰ

Abstract......................................................................................................Ⅱ

第一章 引言 1

1.1亚铜簇合物 1

1.1.1亚铜簇合物的性质 1

1.1.2亚铜簇合物催化及光反应 2

1.1.3碲醚亚铜簇合物 3

1.2乌尔曼C-C偶联反应 4

1.2.1乌尔曼反应 4

1.2.2乌尔曼C-N偶联反应机理的探索 4

1.2.3亚铜簇合物光催化乌尔曼C-N偶联 5

1.2.4亚铜簇合物光催化乌尔曼C-C偶联 5

1.3研究意义 6

第二章 二茂铁碲醚配体的合成 8

2.1 合成路线 8

2.1.1二茂铁碲醚配体L1的合成 8

2.1.2二茂铁碲醚配体L2的合成 8

2.2试剂与仪器 8

2.2.1 试剂 8

2.2.2 仪器 9

2.3 四氢呋喃纯化处理 9

2.4配体L1的合成与纯化 9

2.4.1配体L1的制备 9

2.4.2二茂铁二碲的后处理与柱色谱提纯 10

2.5配体L2的合成与纯化 10

2.5.1配体L2的制备 10

2.5.2配体L2的后处理与柱色谱提纯 11

第三章 亚铜簇合物的合成 12

3.1合成路线....................................................................................12

3.1.1亚铜簇合物[Cu₄I₄(L1)₂(MeCN)₂]的合成....................................12

3.1.2亚铜簇合物[Cu₂I₂(L2)₂]的合成...............................................12

3.2合成亚铜簇合物[Cu₄I₄(L1)₂(MeCN)₂]的步骤......................................12

3.3合成亚铜簇合物[Cu₂I₂(L2)₂]的步骤................................................13

第四章 光催化C-C偶联 14

4.1催化路线 14

4.2操作步骤及后处理 14

4.2.1亚铜簇合物光催化反应步骤 14

4.2.2反应后处理 14

4.2.3对照反应 14

第五章 实验结果 16

5.1单晶结构 16

5.2亚铜簇合物1和2的晶体学数据 17

5.3亚铜簇合物UV-Vis-DRS 图谱分析 18

第六章 结论与展望 19

6.1 实验结论 19

6.2 展望 19

参考文献 20

致谢 23

1. 引言

1.1亚铜簇合物

1.1.1亚铜簇合物的性质

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