臺灣博碩士論文加值系統

近幾十年來二亞胺配位基(??-diketiminate)是很熱門的金屬化合物配位基。因為它和金屬良好的鍵結能力及其旁觀者配位基(spectator ligand)的特性，對於探討小分子活化的研究上是很好的選擇。近年來對於鎳族化合物小分子活化的研究不斷的增加，過往文獻上希望合成出單體鎳族化合物以利於小分子活化的研究。部分文獻利用立障大的取代基來形成單體化合物，另一部分則利用含氮配位基使雙體化合物形成單體化合物。
本篇論文中選用的二亞胺配位基，一邊為立障大的2,6-diisopropylaniline，另一邊則為含氮配位基的alkylpyridine(methyl and ethyl)。希望藉由此二種特性的配位基來得到單體的鎳族化合物。一系列的鎳族化合物藉由不同金屬起始物和二亞胺配位基反應而得。藉由光譜來鑑定其結構及特性，並得到X-ray晶體繞射結構。

During past few decades, the ??-diketiminate is a popular ligand in coordination chemistry, due to it''s good binding ability and spectator ligand property. Several efforts on the synthesize mononuclear nickel-group complexes for small molecule activation were reported but not well studied. One strategy is using steric hindrance ??-diketiminate ligand to synthesize mononuclear metal complexes. Second method ,to introduce more chelate site on the ??-diketiminate ligand to prevent the dimer complexes formation.
We desing the new ??-diketiminate ligands which one part has large steric effect (2,6-diisopropylanile), and another part has nitrogen donor group(methylpyridine and ethylpyridine).They will be good ligands for mononuclear nickel-group complexes. Using these ligands to synthesize mononuclear nickel-group complexes and characterized by spectroscopy and single X-ray crystallography.
 

第一章、緒論 1
1.1 前言 1
1.2 二亞胺配位基 1
1.3 含二亞胺的鎳化合物 2
1.3.1 二亞胺鎳化合物介紹 2
1.3.2 二亞胺鎳化合物立體障礙的影響 8
1.3.3 二亞胺鎳化合物反應性 12
1.4 含二亞胺的鈀化合物 15
1.4.1二亞胺鈀化合物介紹 15
1.4.2二亞胺鈀化合物反應性 18
1.5 含二亞胺的鉑化合物 21
1.5.1 二亞胺鉑化合物介紹 21
第二章、二亞胺鎳族元素化合物合成及鑑定 24
2.1 前言 24
2.2 鎳二價化合物L1NiCl(1)及L2NiCl(2)合成 24
2.2.1鎳二價化合物L1NiCl(1)的合成與鑑定 24
2.2.2 鎳二價化合物L2NiCl(2)的合成與鑑定 32
2.3鎳一價化合物L1Ni(3)的合成與鑑定 36
2.4 鈀二價化合物L1PdCl(4)及L2PdCl(5)的合成 42
2.4.1 鈀二價化合物L1PdCl (4)的合成與鑑定 42
2.4.2 鈀二價化合物L2PdCl (5)的合成與鑑定 47
2.5 鉑二價化合物L1PtCl(6)及L2PtCl(7)的合成 52
2.5.1鉑二價化合物L1PtCl (6)的合成與鑑定 52
2.5.2 鉑二價化合物L2PtCl (7)的合成與鑑定 56
第三章、結論 60
第四章、實驗 61
4.1試藥來源及前處理 61
4.2儀器部分 64
4.3 實驗步驟 65
4.3.1 化合物L1NiCl(1)的合成 65
4.3.2化合物L2NiCl(2)的合成 66
4.3.3化合物L1Ni(3)的合成 67
4.3.4化合物L1PdCl(4)的合成 67
4.3.5化合物L2PdCl(5)的合成 67
4.3.6化合物L1PtCl(6)的合成 68
4.3.7化合物L2PtCl(7)的合成 68
參考文獻 70
附錄 73

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