我們合成出三牙雙苯酚膦螯合配位基bis(3,5-di-tert-butyl-2-hydroxyphenyl)phenylphosphine ([OPO]H2)。利用該配位基和第一族，第四族金屬及錫金屬起始物，反應生成一系列的金屬錯合物。並利用核磁共振光譜、X-Ray結構及元素分析的鑑定，使我們清楚知道這些錯合物的組成及結構。在確定這些金屬錯合物之後，我們更進一步探討這些金屬錯合物對內酯的開環聚合催化活性。

A tridentate diphenolate phosphine ligand H2[OPO] (bis(3,5-di-tert-butyl-2-hydroxyphenyl)phenylphosphine) has been synthesized in high yield. Treatment of H2[OPO] with Ti(OEt)4 in toluene at room temperature produced reddish orange crystalline Ti[OPO]2. The bis-ligand complex Ti[OPO]2 also be obtained from the in situ lithiation of H2[OPO] in THF or toluene followed by addition of TiCl4(THF)2. The reactions of MCl2[N(SiMe3)2]2 (M = Zr, Hf) with H2[OPO] in pentane at room temperature generated cleanly [OPO]2Zr(H2O) and [OPO]2Hf(H2O), respectively, in high yield. Treatment of TiCl4(THF)2 with Ti[OPO]2 in toluene afforded [OPO]TiCl2(THF). The solution and solid-state structures of Ti[OPO]2, [OPO]TiCl2(THF), [OPO]2Zr(H2O) and [OPO]2Hf(H2O) were studied by multinuclear NMR spectroscopy and X-ray crystallography. lithiation of H2[OPO] with n-BuLi in DME solution afforded [OPO]Li2(DME)2. The metathetical reactions of H2[OPO] with NaH or KH in DME solutions, respectively, produced the corresponding complexes [OPO]Na2(DME)2 and {[OPO]K2(DME)2}2. Both [OPO]Li2(DME)2 and [OPO]Na2(DME)2 are highly active catalysts for ring-opening polymerization of caprolactone. A series of tetravalent tin complexes [OPO]SnX2 (X = Cl, Me, n-Bu) also be obtained from the in situ lithiation of H2[OPO] in THF followed by addition of SnCl2X2. A divalent tin complexe [OPO]Sn also be obtained by analogous way from the in situ lithiation of H2[OPO] in pentane followed by addition of SnCl2.

一、 緒論 1
二、 結果與討論 4
1. [OPO]H2的合成與鑑定 4
2. [OPO]Li2(DME)2的合成與鑑定 4
3. [OPO]Na2(DME)2的合成與鑑定 12
4. {[OPO]K2(DME)2}2的合成與鑑定 14
5. [OPO]M2(DME)2 (M=Li or Na) 的催化反應 19
6. [OPO]2Ti的合成與鑑定 21
7. [OPO]TiCl2(thf)的合成與鑑定 25
8. [OPO]2Zr(H2O)的合成與鑑定 31
9. [OPO]2Hf(H2O)的合成與鑑定 34
10. [OPO]2Ti和[OPO]2M(H2O) (M=Zr or Hf)的催化反應 36
11. [OPO]Sn的合成與鑑定 38
12. [OPO]SnCl2(thf)的合成與鑑定 40
13. [OPO]Sn(Me)2的合成與鑑定 41
14. [OPO]Sn(n-Bu)2的合成與鑑定 43
三、 結論 45
四、 實驗部分 46
1. 一般程序 46
2. 儀器 47
3. 實驗步驟 48
(1) 合成H2[OPO] [YNC 3-175] 48
(2) 合成[OPO]Li2(DME)2 [YNC 2-139] 49
(3) 合成[OPO]Na2(DME)2 [YNC 3-23] 51
(4) 合成{[OPO]K2(DME)2}2 [YNC 3-102] 52
(5) 合成[OPO]2Ti [YNC 1-199] 53
(6) 合成[OPO]2Zr(H2O) [YNC 1-196] 55
(7) 合成[OPO]2Hf(H2O) [YNC 1-202] 56
(8) 合成[OPO]TiCl2(thf) [YNC 2-174] 56
(9) 合成[OPO]Sn [YNC 1-254] 57
(10) 合成[OPO]Sn(Me)2 [YNC 1-337] 58
(11) 合成[OPO]Sn(n-Bu)2 [YNC 1-256] 60
(12) 合成[OPO]SnCl3- (HNEt3)+ [YNC 3-98] 61
五、 參考文獻 63
六、 附錄 67
1.其他化合物的合成與鑑定 67
2.變溫NMR光譜圖 68
(1).[OPO]Li2(DME)2的變溫1H NMR光譜[YNC 3-81] 68
(2).[OPO]Li2(DME)2的變溫31P NMR光譜[YNC 3-81] 70
(3).[OPO]Li2(DME)2的變溫7Li NMR光譜[YNC 3-81] 72
(4).{[OPO]K2(DME)2}2的變溫1H NMR光譜[YNC 3-137] 73
(5).[OPO]2Ti的變溫1H NMR光譜[YNC 3-118]....................80
(6).[OPO]2Zr(H2O)的變溫1H NMR光譜[YNC 2-16]…….…82
(7).[OPO]TiCl2(thf)的變溫1H NMR光譜[YNC 3-124] 85
3.Crystallographic Data 89

圖目錄
圖一：多牙配位基示意圖.........................................................................3
圖二：合成[OPO]H2配位基簡圖……………………………………….4
圖三：合成[OPO]Li2(DME)2…………………………………………….5
圖四：[OPO]Li2(DME)2的分子結構……………………………………6
圖五：[OPO]Li2(DME)2 31P{1H} NMR變溫光譜………………………7
圖六：[OPO]Li2(DME)2 7Li{1H} NMR變溫光譜………………………8
圖七：{[OP(OH)]Li(Et2O)}2的分子結構……………….........…………10
圖八：[OPO]2Li4(Et2O)3的分子結構…………………………………...11
圖九：合成[OPO]Na2(DME)2…………………………………………..13
圖十：合成{[OPO]K2(DME)2}2………………………………………..14
圖十一：{[OPO]K2(DME)2}2的分子結構……………………………...16
圖十二：[OPO]Ti2的分子結構…………………………………………21
圖十三：[OPO]2Ti及[OPO]2Zr(H2O) 於300K的1H NMR光譜……….22
圖一四：[OPO]2Ti的1H NMR變溫光譜………………………………..23
圖十五：[OPO]TiCl2(thf)的分子結構…….............................................26
圖十六：[OPO]TiCl2(thf)的1H NMR變溫光譜.......................................28
圖十七：[OPO]2Zr(H2O)的1H NMR變溫光譜…………………….…...33
圖十八：[OPO]2Zr(H2O)的分子結構…………………………….…….33
圖十九：[OPO]2Hf(H2O)的分子結構………………………………….35
圖二十：[OPO]Sn的分子結構………………………………………...38
圖二十一：[OPO]SnCl2(thf)的分子結構…............................................40
圖二十二：[OPO]Sn(Me)2的分子結構....................................................42
圖二十三：[OPO]Sn(n-Bu)2的分子結構. ...............................................44
表格目錄
表一：[OPO]M2(DME)2 (M=Li or Na) 的催化反應..............................20
表二：[OPO]TiCl2(thf) 的催化反應……………………….............…..30
表三：[OPO]2Ti和[OPO]2M(H2O) (M=Zr or Hf) 的催化反應……….37

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