含硫原子配位的後過渡金屬錯合物無論在生物科技或是在工業觸媒上都具有相當程度的應用。在本論文中，成功的合成出四種二牙硫醇配位基2-(Benzylidene)benzenethiol (NS-1)、2-[2,6-(Dimethylbenzylidene)]benz- enethiol (NS-2)、2-(2-Chloro-1-methylethylidene)benzenethiol (NS-3)和2-(
Diphenylphosphanyl)benzenethiol (PS)，以及五種三牙硫醚配位基N-{N-[2- (Diphenylphosphino)benzylidene]-2-sec-butylethylsulfide} (PNS-1)、N-{N-[
2-(Diphenylphosphino)benzylamino]-2-sec-butylethylsulfide} (PNS-2)、2-[2-(
Diphenylphosphino)phenylsulfanylmethyl]pyridine (PSN-1)、2-[2-(Diphenyl- phosphino)phenylsulfanyl]ethylamine (PSN-2)和2-(Diphenylphosphino)phe-
nylsulfanylacetonitrile (PSN-3)，並且分別與數個後過渡金屬鹽類(鋅、銀、鈀、鎳鹽等)反應，得到錯合物1-12。除了光譜鑑定之外，錯合物3、4、5、6、7、8、9、10、11及12亦得到晶體，同時利用X光單晶繞射解析定出其固態結構。從錯合物1-6的光譜鑑定及單晶結構可以發現到，PNS類型三牙基在鋅、銀、鈀、鎳離子中的配位模式皆不相同，鋅錯合物1和2中配位基僅以磷、氮原子去鍵結金屬，而在鈀錯合物3中卻是磷、氮、硫原子皆參與配位，表示硫醚基鍵結到鈀離子上的意願比鍵結到鋅離子上還大。相同的配位基分別經由兩種不同路徑反應，得到配位形式不同的銀錯合物4與5，一為M2L2型之二價雙核錯合物，另一則為ML2型之單核錯合物。與鎳鹽反應更可得到奇特架構之四核鎳錯合物6。PSN-1在錯合物8-10中有兩種不同的配位模式。而PSN-2和銀鹽反應可得到與錯合物4架構相似的雙核銀錯合物11，PSN-3則是以磷、硫原子去配位鈀離子，突顯出PNS及PSN配位基鍵結模式的多變。此外使用PS二牙基和鋅鹽反應，可得到與文獻相異之配位基氧化(L=O)的ML(L=O)型鋅錯合物7。除了NMR、MS、EA和單晶結構的證據之外，常溫以及變溫的NMR光譜亦用來探討部分錯合物溶液結構之變化。

The late transition metal complexes containing sulfide ligands have trem- endous applications not only in biochemistry but also in industrial catalysis. We have successfully synthesized four different bidentate ligands, 2- (Benzylidene)benzenethiol(NS-1), 2-[2,6-(Dimethylbenzylidene)]benzenethi- ol(NS-2), 2-(2-Chloro-1-methylethylidene)benzenethiol(NS-3) and 2-(Diphe- nylphosphanyl)benzenethiol(PS), and five tridentate ligands, N-{N-[2-(Diph- enylphosphino)benzylidene]-2-sec-butylethylsulfide}(PNS-1), N-{N-[2-(Di- phenylphosphino)benzylamino]-2-sec-butylethylsulfide}(PNS-2), 2-[2-(Diph- enylphosphino)phenylsulfanylmethyl]pyridine(PSN-1), 2-[2-(Diphenylphos- phino)phenylsulfanyl]ethylamine(PSN-2) and 2-(Diphenylphosphino)phenyl- sulfanylacetonitrile(PSN-3). These ligands reacted with the late transition metal (Zn, Ag, Pd, and Ni) salts, and produced complexes 1-12. Besides their spectra, we also obtained crystal structures of complexes 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12. We found that the PNS tridentate ligands had different bonding modes in zinc, silver, palladium, and nickel complexes. For examples, in zinc complexes 1 and 2 only P and S atoms were coordinated to the metal while all P, N, and S atoms were coordinated to the Pd metal in Pd complexes. It indicated that thiolether prefers to coordinate to palladium but not to zinc in our cases. When PNS-2 went through different reaction routes, two silver complexes 4 and 5 with different coordination modes a M2L2 type dinuclear complex and a ML2 type mononuclear complex were obtained.. When reacting PNS-2 with nickel, we obtained an unique tetranuclear nickel complex 6. PSN-1 showed two different coordinate modes in complexes 8-10 while PSN-2 and silver produced a dinuclear silver complex 11 that resembled complex 4. PSN-3 coordinated to Pd ion by phosphorus and sulfide atoms. As such, we demonstrated the various coordinated modes in PNS and PSN ligands. Finally PS bidentate ligand reacted with zinc salt produced complex 7 with one oxidized ligand. The variable temperature NMR experiment was also used to probe the structural change that occurred in solution state for 3.

目錄
謝誌
授權書
提要 i
目錄 iv
圖目錄 vii
表目錄 x
附錄 xi
壹、 緒論 1
一、前言 1
二、半安定配位基之介紹與應用 1
三、含磷配位基之鈀、鎳錯合物在催化領域的應用 9
四、含磷配位基之鋅錯合物在生化領域的應用 11
五、鋅化物在工業觸媒之應用 22
六、含磷、氮、硫三芽配位基金屬錯合物之應用 25
七、本文配位基之介紹 27
貳、 實驗部分 30
一、儀器 30
二、藥品及純化 31
三、實驗步驟 37
參、 結果與討論 57
一、配位基之合成及性質探討 57
(1) NS配位基 57
(2) PS配位基 61
(3) PNS配位基 63
(4) PSN配位基 65
二、錯合物之合成及性質探討 69
(1) 錯合物ZnCl2(PNS-1) / 1的合成探討 69
(2) 錯合物[PdCl(PNS-2)]Cl / 3的合成與結構探討 71
(3) 錯合物[Ag2(PNS-2)2](ClO4)2 / 4的合成與結構探討 76
(4) 錯合物[Ag(PNS-2)2](ClO4)2 / 5的合成與結構探討 79
(5) 錯合物[Ni4Cl2(PNS-2)2(Ph2P(O)C6H4CH2NHC2H4S)2
](ClO4)2 / 6的合成探討 83
(6) 錯合物Zn(OPS)(PS) / 7的合成與結構探討 89
(7) 錯合物ZnCl2(PSN-1) / 8的合成與結構探討 91
(8) 錯合物PdCl2(PSN-1) / 9的合成探討 95
(9) 錯合物Ag(PSN-1)ClO4 / 10的合成與結構探討 99
(10)錯合物[Ag2(PSN-2)2](ClO4)2 / 11的合成與結構探
討 101
(11)錯合物PdCl2(PSN-3) / 13的合成與結構探討 105
三、錯合物之綜合探討 108
(1) 錯合物4和錯合物5之綜合探討 108
(2) 錯合物4和錯合物11之結構探討 112
(3) 錯合物8、錯合物9和錯合物10之綜合探討 114
肆、 結論 116
伍、 參考文獻 119
陸、 附錄 124
柒、 其他合成出之化合物 328

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