我們成功合成出三腳架型四牙配位基H3[O3P] (tris-(3,5-di-tert- butyl-2-hydroxy-phenyl)phosphine)，並利用配位基H3[O3P]對等當量三價鋁一系列金屬起始物反應可合成相關的三角架構形金屬錯合物，經由NMR和X-ray鑑定化合物的結構組成。配位基H3[O3P]和三價鋁金屬起始物反應所產生的金屬化合物為[O3P-H]AlR，[O3P-H]AlR是一個兩性離子型金屬錯合物(zwitterionic complexes)，在配位基分子中三苯酚基磷的磷原子上有一個酸性氫，我們對此特性做一些實驗和探討，最後並把氫取代基置換成甲基取代，合成出[O3P-Me]AlR一系列鋁金屬錯合物。
在[O3P-Me]AlR金屬錯合物合成方面，我們也可以先修飾原本配位基H3[O3P]合成出H3[O3P-Me]OTf三腳架型三牙配位基，並利用此配位基H3[O3P-Me]OTf對等當量三價鋁一系列金屬起始物反應，由NMR和X-ray鑑定化合物的結構組成。

除了鋁金屬外，我們也利用配位基H3[O3P]對鉭、鈷、鎳、錫和錳等金屬作螯合反應的測試並探討其合成結果與其化合物結構相關性。

We utilized the tripodal ligand (tris-(3,5-di-tert-butyl-2-hydroxy-phenyl)- phosphine) H3[O3P] to react with 1 equiv of AlR3 (R = Cl, Me, Et, iBu and OiPr). From NMR and X-ray data proved, we could give the stable Al(III) complexes [O3P-H]AlR (R = Cl, Me, Et and iBu). [O3P-H]AlR is a zwitterionic complexes. Because the phenolato phosphine ligand bond a proton at the phosphorous, and Al(III) coordinated three RO- (tris phenolate group) and one alkyl- substituent group. So the Al(III) metal could be carried -1 charge and the phosphorous could be carried +1 charge. When H3[O3P] reacted with AlR3, the original trisphenolato phosphine ligand ([O3P]3-) was changed into a trisphenoato phosphonium ligand ([O3P-H]2-).

The [O3P-H]AlMe in the trisphenoato phosphonium group has a proton, and we attempted to use a bese to deprotonate the acidic proton. We chose n-BuLi to react with [O3P-H]AlMe, and successfully gave {[O3P:]AlMe}- ionic complexe. In the {[O3P:]AlMe}- complexe, the lone pair electron of phenolato phosphine group is a nucleophile,It reacted with MeOTf of electrophile. The product of the reaction could give [O3P-Me]AlMe.In this reactions, the original trisphenoato phosphonium ligand ([O3P-H]2-) was changed into a new methyl trisphenoato phosphonium ligand ([O3P-Me]2-). We could utilize H3[O3P] to react with 1 equiv MeOTf in diethyl ether, and gave a new tripodal ligand {H3[O3P-Me]}OTf. Also, we utilized the {H3[O3P-Me]}OTf to react with 1 equiv of AlR3 (R = Cl, Me, Et and iBu). We gave that Al(III) complexes [O3P-Me]AlR (R = Cl, Me, Et and iBu).

一、 緒論..............................................................................8
二、 結果與討論................................................................12
(一). H3[O3P]的合成.........................................................12
(二). H3[O3P]和Ta(V) 之反應和討論..............................12
1. 合成和鑑定Ta[(OPO)OH]2Cl......................................13
2. 合成和鑑定Ta[(OPO)OH]Cl3......................................17
3. 合成和鑑定Ta[O3P]Cl2...............................................20
4. 有關 Ta[O3P]Cl2測試反應..........................................22
(三). H3[O3P]和Sn(IV)之反應和討論..............................24
1. 合成和鑑定Li(THF)4{SnCl3[(OPO)OH]}...................29
2. 合成和鑑定[(OPO)OH]SnClR(THF) R = n-Bu, Ph...34
3. 金屬交換反應.................................................................39
(四). H3[O3P]和Al(III)之反應跟和討論............................43
1. 合成和鑑定 [O3P-H]AlCl and [O3P-H]AlMe...............45
2. 合成和鑑定[O3P-H]AlR (R = Et, OiPr, iBu)................48
3. Deprotonation of [O3P-H]AlMe...................................53
4. Deprotonation and Alkylation of [O3P-H]AlCl...........59
5. 合成和鑑定[O3P-Me]AlR (R = Cl, Me, Et and iBu)........66
(五). H3[O3P]和Ni(II)、Co(II)、Mn(II)、Cu(II) 之反應和討論：
.................75
1. 合成和鑑定M[(OP)(OH)2]2 M = Ni and Co....................78
2. 合成和鑑定 [(OPO)(μ-OLi)]2Ni2(THF)2 and Mn[(LiO2P)-
(μ-OLi)]2(THF)3..........................................................81
三、 結論......................................................................89
四、 實驗部分.....................................................................90
1. 一般程序...................................................................90
2. 儀器..................................................................................90
3. 實驗步驟..........................................................................92
(1). 合成H3[O3P]...........................................................92
(2). 合成TaCl[(OPO)OH]2..............................................93
(3). 合成Ta[(OPO)OH]Cl3.............................................95
(4). 合成Ta[O3P]Cl2..........................................................95
(5). 合成Li(THF)4{SnCl3[(OPO)OH]}..............................97
(6). 合成[(OPO)OH]SnCl(n-Bu)(THF)............................98
(7). 合成[(OPO)OH]SnCl(C6H5)(THF)..........................99
(8). 合成[HO(O2P=O)]2Fe2(μ-Cl)Cl(THF)....................100
(9). 合成[O3P-H]AlCl....................................................101
(10). 合成[O3P-H]AlMe....................................................102
(11). 合成[O3P-H]AlEt.....................................................103
(12). 合成[O3P-H]AliBu...................................................105
(13). 合成[O3P-H]AlOiPr 和[O3P-H]AlOiPr(HOiPr).....106
(14). 合成{[O3P:]AlMe}Li(DME)3..................................107
(15). 合成[O3P-Me]AlMe................................................108
(16). 合成[O3P-Me]AlCl..................................................110
(17). 合成[O3P-Me]AlnBu...............................................112
(18). 合成{H3[O3P-Me]}Otf............................................113
(19). 合成[O3P-Me]AlEt................................................115
(20). 合成[O3P-Me]AliBu.................................................115
(21). 合成Ni[(OP)(OH)2]2...............................................117
(22). 合成Co[(OP)(OH)2]2(THF)...................................118
(23). 合成[(OPO)(μ-OLi)]2Ni2(THF)2.........................119
(24). 合成Mn[OP(OLi2)2]2(THF)3.................................121
五、 參考文獻..................................................................123
六、 附錄..........................................................................128
1. Cystallographic Data..................................................128

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