我們合成出三苯酚磷螫合配位基(tris-(3,5-di-tert-butyl-2-hydroxy-phenyl)phosphine)([O3P]H3)與鋁金屬形成錯合物[O3PMe]AlR(R = OtBu、OPh)，並利用核磁共振光譜、晶體繞射分析以及元素分析的鑑定，確定此類化合物的組成與結構。同時將與ε-caprolactone 進行高分子開環聚合反應(ring opening polymerization)，討論催化劑的反應性，並利用DFT 理論計算，模擬分子結構，討論立體障礙對於開環聚合反應之影響。利用化合物[O3PMe]AlR(R = Cl、Me、OtBu、OPh)測量UV、PLE，與利用DFT 理論計算，模擬分子的電子組態，討論電化學的特性。
合成出新的雙苯酚磷螫合配位基bis(3,5-tert-butyl-2-phenoxy) tert-butylphosphine([tBuOPO]H2)，與第一族金屬起始物，如n-BuLi、NaH、KH 形成一系列的金屬錯合物[tBuOPO]M2(Solvent)x (M = Li、Na、K)。並利用核磁共振光譜、晶體繞射分析以及元素分析的鑑定，確定此類錯合物dimeric 的組成及結構。並利用{[tBuOPO]Li2(DME)}2 與第四族金屬起始物TiCl3、MCl4(THF)2 (M = Ti、Zr、Hf)，利用不同的反應條件，形成[tBuOPO]2M、[tBuOPO]MCl2(THF) (M = Ti、Zr、Hf)，除了鑑定分子結構與組成，也進一步合成具有烷氧基之第四族金屬錯合物進行高分子開環聚合反應的測試，討論其反應性。也與鉭金屬形成錯合物[tBuOPO]2TaX (X = F、Cl)，同時發現降低反應的濃度，能夠合成出[tBuOPO]TaCl3，得到不同的結果。也試著合成釩、鉻錯合物，目前尚缺乏數據支持，無法確定結構。

Aluminum complexes, [O3PMe]AlR(R = OtBu, OPh), containing tris-(3,5-di-tert-butyl-2-hydroxy-phenyl)phosphine ([O3P]H3) which is a novel tridentate ligand have been synthesized and characterized by NMR, X-ray diffraction and elemental analysis. Theses complexes were used as catalysts for ring-opening polymerization of ε-caprolactone. We suggested that the stereo effect of catalysts is the main factor in the ring-opening polymerization and compared the mechanism with DFT. In additional, we studied the electronic states and electronic chemistry of [O3PMe]AlR by DFT, UV and PLE.
The novel ligand, bis(3,5-tert-butyl-2-phenoxy) tert-butylphosphine ([tBuOPO]H2), reacted with alkali metals such as n-BuLi, NaH and KH to form a series metal complexes, [tBuOPO]M2(Solvent)x (M = Li, Na, K). These metal complexes are all dimeric molecules characterized by X-ray diffraction, NMR and elemental analysis. Moreover, we reacted {[tBuOPO]Li2(DME)}2 with metal complexes of group 4, TiCl3 and MCl4(THF)2 (M = Ti, Zr, Hf), and we received [tBuOPO]2M and [tBuOPO]MCl2(THF) (M = Ti, Zr, Hf). We also synthesized alkoxide complexes of the series metal complexes and studied the catalytic reactivity for ring-opening polymerizations. Furthermore, tantalum complexes, [tBuOPO]2TaX (X = F, Cl) and [tBuOPO]TaCl3, have been synthesized and characterized. Especially synthesizing [tBuOPO]TaCl3 should be carefully controlled by lowering the concentration of TaCl5.

壹、 三苯酚膦化物鋁錯合物 ............................................................................................................... 1
一、 緒論 ......................................................................................................................................... 1
二、 結果與討論 .............................................................................................................................. 4
1. [O3PMe]AlR (R=Cl、Me、OtBu、OPh)的合成與反應性 .................................................... 4
1.1 [O3PMe]AlR (R = OtBu、OPh)的合成與鑑定 ....................................................................... 4
1.2 [O3PMe]AlR 的ε-caprolactone 開環聚合反應與討論 ............................................................ 7
1.3 [MeO3PMe]AlOtBu 的分子結構模擬 ..................................................................................... 10
1.4 [MeO3P]H3 的合成 ................................................................................................................... 11
2 [O3PMe]AlR (R=Cl、Me、OtBu、OPh)的光物理測定與討論 .......................................... 13
三、 結論 ....................................................................................................................................... 16
四、 實驗部分 ............................................................................................................................... 17
1 一般程序 ............................................................................................................................... 17
2 儀器 ....................................................................................................................................... 17
3 實驗步驟 ............................................................................................................................... 19
(1) 合成[O3PMe]AlOtBu (YLH-1-135) .......................................................... 19
(2) 合成NaOPh (YLH-1-131) ........................................................................ 20
(3) 合成[O3PMe]AlOPh (YLH-1-197) ........................................................... 20
(4) ε-caprolactone 開環聚合反應 ...................................................................... 21
(5) 合成2-bromo-4,6-dimethylphenol (YLH-1-277) ..................................... 21
(6) 合成[MeO3P]H3 (YLH-1-279) .................................................................... 22
貳、 雙苯酚磷化物金屬錯合物 ......................................................................................................... 23
一、 緒論 ....................................................................................................................................... 23
二、 結果與討論 ............................................................................................................................ 26
1 [tBuOPO]H2 的合成與討論 ................................................................................................... 26
2 [tBuOPO]H2 第一族錯合物的合成與討論 ........................................................................... 27
3 [tBuOPO]H2 第一族錯合物的ε-caprolactone 開環聚合反應與討論 ................................... 38
4 [tBuOPO]H2 第四族錯合物的合成與討論 ........................................................................... 42
5 [tBuOPO]H2 第四族錯合物的ε-caprolactone 開環聚合反應與討論 ................................... 61
6 [tBuOPO]H2 鉭錯合物的合成與討論 ................................................................................... 70
7 [tBuOPO]H2 釩、鉻錯合物的合成與討論 ........................................................................... 73
三、 結論 ....................................................................................................................................... 75
四、 實驗部分 ............................................................................................................................... 77
1 一般程序 ............................................................................................................................... 77
2 儀器 ....................................................................................................................................... 77
3 實驗步驟 ............................................................................................................................... 78
(1) 合成[tBuOPO]H2 (YLH-1-96) .................................................................. 78
(2) 合成{[tBuOPO]Li2(DME)}2 (YLH-1-308) ............................................... 79
(3) 合成{[tBuOPO]Na2(DME)2.5}2 (YLH-1-310) .......................................... 80
(4) 合成{[tBuOPO]K2(THF)2}2 (YLH-1-312) ................................................ 81
(5) 合成TiCl4(THF)2 (YLH-1-275) ................................................................ 82
(6) 合成[tBuOPO]2Ti (YLH-1-348) ................................................................ 82
(7) 合成[tBuOPO]TiCl2(THF) (YLH-2-74) .................................................... 84
(8) 合成ZrCl4(THF)2 (YLH-2-51) ................................................................. 85
(9) 合成[tBuOPO]2Zr (YLH-2-60) ................................................................. 85
(10) 合成[tBuOPO]ZrCl2(THF) (YLH-2-132) ................................................. 86
(11) 合成HfCl4(THF)2 (YLH-2-51) ................................................................. 87
(12) 合成[tBuOPO]2Hf (YLH-2-94) ................................................................. 87
(13) 合成[tBuOPO]HfCl2(THF) (YLH-2-133) ................................................. 88
(14) 合成[tBuOPO]TiCl(OtBu) (YLH-3-24) .................................................... 89
(15) 合成[tBuOPO]Ti(OtBu)2 (YLH-2-298) ..................................................... 89
(16) 合成[tBuOPO]ZrCl(OtBu)(THF) (YLH-2-262) ........................................ 90
(17) 合成[tBuOPO]Zr(OtBu)2(THF) (YLH-2-302) .......................................... 90
(18) 合成[tBuOPO]HfCl(OtBu)(THF) (YLH-2-281) ....................................... 91
(19) 合成[tBuOPO]Hf(OtBu)2(THF) (YLH-2-268) .......................................... 92
(20) 合成[tBuOPO]Ti(OiPr)2 (YLH-3-29) ........................................................ 93
(21) 合成[PhOPO]Ti(OiPr)2 (YLH-3-66) ......................................................... 93
(22) ε-caprolactone 開環聚合反應 ...................................................................... 94
(23) 合成[tBuOPO]2TaCl (YLH-2-39) ............................................................. 94
(24) 合成[tBuOPO]TaCl3 (YLH-2-87) ............................................................. 95
(25) 合成[tBuOPO]2TaF (YLH-2-40) ............................................................... 96
(26) 合成1x [tBuOPO]Ti(OiPr)2 + 1x ε-CL (YLH-3-141) .............................. 97
參、 參考文獻 .................................................................................................................................... 97
肆、 附錄 .......................................................................................................................................... 104
一、 ATRP 催化反應 ........................................................................................................................ 104
二、 Crystallographic Data ................................................................................................................ 107
三、 DFT 理論計算 ............................................................................................................................ 109
1. Cartesian Coordinates for [tBuOPO]Ti(OiPr)2...................................................................... 109
2. Cartesian Coordinates for [PhOPO]Ti(OiPr)2 ....................................................................... 112
3. Cartesian Coordinates for [O3PMe]AlOtBu .......................................................................... 114
4. Cartesian Coordinates for [MeO3PMe]AlOtBu ...................................................................... 118
5. Cartesian Coordinates for [O3PMe]AlCl .............................................................................. 120
6. Cartesian Coordinates for [O3PMe]AlMe ............................................................................ 123
7. Cartesian Coordinates for [O3PMe]AlOPh ........................................................................... 126

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