新型的螯合配位基，Me[NOON]H2，已經成功地被合成出來了，並且藉由核磁共振光譜可以確認其結構。利用n-BuLi 與配位基進行反應可以合成出具有雙苯胺配位基的鋰鹽錯合物，並且由核磁共振光譜的氫譜圖可以得知其為一具有ether adduct 的產物。將此鋰金屬錯合物與Ti(OiPr)4 及TiCl4(THF)2 反應可以得到其鈦金屬錯合物，分別為MeNOONTi(OiPr)2 和MeNOONTiCl2，而這些金屬錯合物可以藉由核磁共振光譜及X-ray 繞射確認其結構。所合成出的這些雙苯胺鈦金屬錯合物之後將作為lactide 及caprolactone 進行開環聚合反應的催化劑。

具有雙苯酚膦螯合配位基的鉭金屬錯合物已經成功的合成出來，可以藉由核磁共振光譜，X-ray 繞射及元素分析確認其結構。具有雙苯酚膦螯合配位基的鉭金屬錯合物是藉由具有不同取代基的格林鈉試劑與[tBuOPO]2TaCl 進行反應。合成出來的鉭金屬錯合物日後將應用在氮分子的活化上。

The novel chelating ligand, Me[NOON]H2 (N,N'-((ethane-1,2-diylbis(oxy))-bis(ethane-2,1-diyl))- bis(2,6-dimethylaniline)), have been synthesized successfully
and characterized by NMR. The lithium complexes of the aryl diamide ligand have also been synthesized by n-BuLi react with neutral ligand, Me[NOON]H2. And the
lithium complexes is a ether adduct according to the 1H NMR. The lithium complex, Me[NOON]Li2(OEt2) react with Ti(OiPr)4 and TiCl4(THF)2 to form the NOON titanium alkoxide and dichloride complexes respectively, and they have been characterized by
1H NMR and X-ray diffraction. These NOON titanium complexes are expected to be a catalyst for the ring opening polymerization of lactide or caprolactone in the future.

The tantalum complexes of diphenolate phosphine ligands have been synthesized and characterized successfully by NMR, X-ray diffraction, and elemental analysis. The tantalum complexes, [tBuOPO]2TaX (X=Me, Et, H) is produced by the reaction of
[tBuOPO]2TaCl with Grignard reagent (MeMgBr and EtMgCl) and superhydride(LiHBEt3). These tantalum complexes will be applied in dinitrogen activation in the
future work.

目錄
論文審定書 ........................................................................................................................i
謝誌 ................................................................................................................................. ii
中文摘要 ......................................................................................................................... iii
Abstract .............................................................................................................................iv
目錄 .................................................................................................................................. v
圖目錄 ..............................................................................................................................ix
表目錄 ............................................................................................................................ xii
壹、雙苯胺鈦錯合物 ....................................................................................................... 1
一、緒論 ................................................................................................................... 1
二、結果與討論 ..................................................................................................... 16
(一) Me[NOON]H2 的合成與討論 .................................................................. 16
(二) Me[NOON]Li2(OEt2)的合成與討論 ........................................................ 19
(三) Me[NOON]Ti(OiPr)2 的合成與討論 ........................................................ 21
(四) Me[NOON]TiCl2 的合成與討論 .............................................................. 26
三、結論 ................................................................................................................. 28
四、實驗部分 ......................................................................................................... 28
vi
1. 一般程序 .................................................................................................... 28
2. 儀器 ............................................................................................................ 28
3. 實驗步驟 .................................................................................................... 29
(1) 合成Me[NOON]H2 (TTT-3-19) ........................................................ 29
(2) 合成Me[NOON]Li2(OEt2) (TTT-3-81) ............................................ 30
(3) 合成Me[NOON]Ti(OiPr)2 (TTT-3-100) ........................................... 30
(4) 合成Me[NOON]TiCl2 (TTT-3-267) ................................................. 31
貳、雙苯酚膦化物鉭錯合物 ......................................................................................... 32
一、緒論 ................................................................................................................. 32
二、結果與討論 ..................................................................................................... 37
(一) [tBuOPO]2TaR (R=Me、Et)的合成與討論 ........................................... 37
(二) [tBuOPO]2TaH 的合成與討論 ................................................................ 47
三、結論 ................................................................................................................. 51
四、實驗部分 ......................................................................................................... 52
1. 一般程序 .................................................................................................... 52
2. 儀器 ............................................................................................................ 52
3. 實驗步驟 .................................................................................................... 53
vii
(1) 合成[tBuOPO]2TaMe (TTT-2-123).................................................. 53
(2) 合成[tBuOPO]2TaEt (TTT-2-124) ................................................... 54
(3) 合成[tBuOPO]2TaH (TTT-2-81) ...................................................... 55
參、參考文獻 ................................................................................................................. 56
肆、附錄 ......................................................................................................................... 64
一、[(MeO3P)Al]2O 的合成與討論 ....................................................................... 64
伍、NMR 光譜圖 ......................................................................................................... 175

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