三-2-硫酚磷基(P(C6H4-2-SH)3, PS3)這配位子在早期(1989年)即被化學家設計出來。起初單純是為了設計多芽的磷硫配位子，近年來，因其多硫的特性有一些的化學家將其用來作酵素的模擬﹔亦有部分的學者利用含磷硫的特性設計合成出新穎的金屬錯合物。本論文主要在探討鍺及錫金屬化合物與三-2-硫酚磷配位子(PS3)反應產物的結構探討。這類產物的晶體結構極為特殊，像四氯化鍺與PS3反應可得具有連續π－π堆疊的超分子結構。若是用三氯甲基鍺則會生成旋光晶體，而非一般之消旋晶體結構。四氯化錫的錯合物與甲醇反應得到了六配位而以甲氧基和PS3上一個硫醇基橋接的雙聚合錫錯合物(Sn(OMe)(PS3))2。而以三氯乙基錫和三氯丁基錫與PS3反應後，藉由昇華(140oC , 10-2torr)均可得到還原消去的產物，且這兩產物外形極為相似但其骨架排列卻大不相同。

Tri(2-thiophenyl)phosphine (P(C6H4-2-SH)3,PS3) was designed at 1989. Recently chemists use this ligand for enzyme models because it provides rich sulfur environment. Some chemists use PS3 to synthesize novel metal complexes. This thesis deals with the synthesis and structural discussion of germanium and tin complexes bearing PS3 ligands. Reactions with different metal source all yield novel structures. Reaction of GeCl4 with PS3 gives supramolecular structures with continuous π-π interaction. Similar reaction with GeCl3Me gives crystals in optically active form in stead of the usual optically inactive racemic form. Reaction with SnCl4 gives six-coordinate dimmeric tin complex (Sn(OMe)(PS3))2 with bridging methoxyl group and thiolate group (from PS3). Reactions using SnCl3Et or SnCl3Bu as metal sources followed by sublimation (140oC , 10-2torr) give reductive elimination products with alkyl groups transferred onto sulfur atom. These two structures are similar in morphology but different in skeletal arrangement.

謝誌 I
授權書 ii
提要 iii
目錄 iv
圖目錄 vii
表目錄 x
附錄 xi
壹、 緒論 1
一、前言 1
二、含硫多芽配位基在生化上之介紹與應用 4
三、含硫磷配位子之介紹與應用 8
四、研究動機 15
貳、 實驗部分 17
一、儀器部分 17
二、藥品及純化 19
三、實驗步驟 22
參、 結果與討論 28
一、PS3與鍺錯合物的合成與結構討論 28
(1) PS3配位子的合成與結構探討 28
(2)錯合物GeCl(PS3) (1)的合成與結構探討 30
(3)錯合物GeEt(PS3) (2)的合成與結構探討 37
二、PS3與錫錯合物的合成及結構探討 40
(1) 錯合物SnCl(PS3)(3)，Sn(OMe)PS3(4)的合成與結構探討40
(2) 錯合物SnBu(PS3)(5)，Sn(PS2SBu)(6)的合成與結構探討44
(3) 錯合物SnMe(PS3)(7)，Sn(PS2SMe)(8)的合成與結構探討51
三、錯合物之綜合探討 54
(1) 錯合物(1)、(2)、(3)、(5)、(7)之31P-NMR光譜探討 55
(2) 錯合物 (1)和錯合物 (2)之綜合探討 57
(3) 錯合物 (6)與錯合物(8)之綜合探討 61
肆、 結論 64
伍、 參考文獻 65
陸、 附錄 67

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