此次論文將介紹本實驗室利用新型配位子[Ph-PNP=N-R](R= C6H3iPr2,Tol)，成功合成並鑑定一系列以[Ph-PNP=N-R](R= C6H3iPr2)為配位基的銅、鐵、鋰錯合物以及以[Ph-PNP=N-R](R=Tol)為配位基的銅、鐵、鋰、鎳錯合物，並利用CV、UV/Vis 光譜、NMR 光譜、DPV 以及X 光單晶繞射分別做結構鑑定的分析與化性、物性的探討。

Nitrogen ligands with bulky substituents are currently attracting interest as tools for controlling the coordination gap aperture. Bis(imino)pyridines and a-diimines are particularly noteworthy in this context. It has been shown that bulky derivatives of N-ligands are highly sensitive to the rates of both chain propagation and of termination processes in polymerization, leading to high molecular weight polyolefins while sterically less demanding analogues produce oligomers. These results underline the importance of steric factors in designing the structure of ligands. Coordination chemistry with the tridentate hybrid ligand containing soft and hard backbone, such as P/N, N/N, etc, has been drawing an intensive research. We have endeavored to prepare a series of amido phosphinimine derivatives containing bulky substituents on both P- and N- atoms and their metal complexes. These complexes which have been well-characterized by solution multi nuclei NMR spectroscopic data and single crystal X-Ray diffractometer are potentially more rigid and robust to conquer the flexibility of the backbone.

壹、前言 ............................................................................................................................ 1
苯胺膦亞胺化(Amido Phosphinimine)衍生物之特性 ............................................. 1
貳、結果與討論 ................................................................................................................ 2
銅化合物的合成與鑑定 ........................................................................................... 2
一、H[Ph-PNP=NC6H3iPr2]與[Ph-PNP=NC6H3iPr2]Li 合成與鑑定 ................ 2
二、[Ph-PNP=NC6H3iPr2]Cu 合成與鑑定........................................................ 8
三、[Ph-PNP=NC6H3iPr2]CuCl 合成與鑑定 .................................................. 10
四、H[Ph-PNP=N-Tol]、[Ph-PNP=N-Tol]Li、[Ph-PNP=N-Tol]Cu 的合成及溶液結構探討 ........................................................................................... 12
五、[Ph-PNP=N-Tol]CuOTf 的合成與鑑定 ................................................... 14
六、銅錯合物的光物理性質 .......................................................................... 17
鐵化合物合成與鑑定 ............................................................................................. 23
一、[Ph-PNP=N-Tol]FeCl 的合成與鑑定 ...................................................... 23
二、[Ph-PNP=N-Tol]FeCl2 的合成與鑑定 ..................................................... 27
三、[Ph-PNP=NC6H3iPr2]FeCl2 合成與鑑定 .................................................. 30
四、[Ph-PNP=N-Tol]FeCl 與[Ph-PNP=N-Tol]FeCl2 的光化學性質 ............. 36
鎳化合物合成與鑑定 ............................................................................................. 36
一、[Ph-PNP=N-Tol]NiCl 的合成與鑑定 ...................................................... 36
電化學探討 ............................................................................................................. 40
參、結論 .......................................................................................................................... 47
肆、實驗步驟 .................................................................................................................. 48
一、一般程序 ......................................................................................................... 48
二、合成 2,6-diisopropylphenyl azide15 ................................................................ 49
三、合成2,4,6-trimethylphenyl azide15 ................................................................. 50
四、合成p-tolyl azide15 .......................................................................................... 51
五、合成H[Ph-PNP=NC6H3iPr2] (JJ 2-47) ........................................................... 52
六、合成[Ph-PNP=NC6H3iPr2]Li(JJ 2-338) ........................................................... 53
七、合成[Ph-PNP=NC6H3iPr2]Cu (JJ 1-244) ......................................................... 54
八、合成[Ph-PNP=NC6H3iPr2]CuCl(JJ 2-67) ........................................................ 55
九、合成[Ph-PNP=NC6H3iPr2]FeCl2(JJ 2-239) ..................................................... 56
十、合成H[Ph-PNP=N-Tol] (JJ 2-278) ................................................................. 56
十一、合成[Ph-PNP=N-Tol]Li (JJ 2-318) ............................................................. 58
十二、合成[Ph-PNP=N-Tol]Cu (JJ 2-342) ............................................................ 58
十三、合成[Ph-PNP=N-Tol]NiCl(JJ 2-262) .......................................................... 60
十四、合成[Ph-PNP=N-Tol]FeCl .......................................................................... 60
十五、合成[Ph-PNP=N-Tol]FeCl2(JJ 2-368) ......................................................... 61
十六、合成[Ph-PNP=N-Tol]CuOTf(JJ 2-344) ....................................................... 62
十七、催化反應的測試 ......................................................................................... 62
伍、附錄([Ph-PNP=N-Tol]FeCl 的還原反應測試) ....................................................... 62
一、[Ph-PNP=N-Tol]FeCl 與Na(s)的反應性測試 ............................................... 63
二、KC8 的合成 17 ................................................................................................. 63
三、[Ph-PNP=N-Tol]FeCl 與KC8 的反應性測試 ................................................. 64
X-Ray Crystallographic Data(L=[Ph-PNP=NC6H3iPr2]) ................................................. 65
X-Ray Crystallographic Data(L’=[Ph-PNP=N-Tol]) ....................................................... 67
參考文獻 ......................................................................................................................... 68

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