臺灣博碩士論文加值系統

碳烯之重元素相似物的性質及配位特性已經被研究了數十年，且有著卓越的研究成果，並且可取代碳烯作為過渡金屬之配位基。由於碳烯之重元素相似物的反應性十分強烈，故需要利用立障效應以及電子效應來對其進行保護使其穩定，所以在碳烯之重元素相似物的研究中，又以氮異雜環所穩定的化合物最多。然而單牙氮異環碳烯重元素雖已有不少研究，但是多牙氮異環碳烯之重元素相似物卻是十分少見。因此我們期望能夠合成具有高對稱性多牙氮異環碳烯重元素相似物，利用苯基以及二苯甲基作為氮上取代基來提供立障，利用氮上面的孤對電子來穩定碳烯之重元素相似物，並使用三亞苯作為分子骨架來達到對稱性的目的。而其中鍺烯、錫烯以及鉛烯的合成是可以利用二價的鍺、錫、鉛的前驅物進行取代反應來獲得，並且以異核核磁共振光譜以及晶體結構來證明其存在。在本研究中，我們成功地合成出多個鍺烯、錫烯、及鉛烯，其中有部份分子都有結構鑑定，並期望之後可以測試其各種反應性，發展其在化學上的各種可能性。

Group 14 metallylenes have been studied for decades and used as replacement of carbene ligands in transition metal complexes. Like the carbene species, one of the synthetic strategies to prepare stable metallylene is to utilize N-heterocycles to stabilize the reactive divalent derivatives. Such strategy has resulted in isolation of several stable monotopic metallylenes. However, it has never been utilized for the synthesis of tritopic metallylenes. The triphenylene molecule is selected as the molecular backbone for planar tris-metallylenes. The rigid backbone can prevent not only the formation of chelating metal complexes, but also the oxidation of the precursors, triphenylene-based hexaamines. Except of the silylene, we successfully synthesized tritopic N-heterocyclic metallylenes, such as germylene, stannylene and plumbylene. Besides, we found the optical bandgap of phenyl-substituted tris-germylene and tris-stannylene drastically red-shifted in crystalline form as a result of crystal packing, showing the unique properties of the tris-germylene and tris-stannylene.

中文摘要 i
ABSTRACT ii
CONTENTS iii
LIST OF FIGURES v
LIST OF SCHEMES vii
LIST OF TABLES viii
Chapter 1 Introduction 1
1.1 Carbene 1
1.2 Metallylenes 2
1.2.1 Silylene 3
1.2.2 Germylene 4
1.2.3 Stannylene 5
1.2.4 Plumbylene 7
1.3 Reactivity of Metallylenes 10
1.4 Research Objective 12
Chapter 2 Molecular Design and Synthetic Methods 13
2.1 Molecular Design 13
2.2 Synthetic Methods 16
Chapter 3 Results and Discussion 18
3.1 Synthesis of Hexaminotriphenylenes 18
3.2 Synthesis of N-Heterocyclic Silylenes 19
3.3 Synthesis of N-Heterocyclic Germylenes 21
3.4 Synthesis of N-Heterocyclic Stannylenes 25
3.5 Synthesis of N-Heterocyclic Plumbylenes 30
3.6 Photophysical Properties of N-heterocyclic Metallylenes 32
3.7 Aromaticity of tris-metallylenes 38
Chapter 4 Conclusions 41
Chapter 5 Experimental Section 42
REFERENCES 52
Appendix 57

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