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研究生： 林宗翰
論文名稱： 具三甲基矽基之磷硫多牙基的新穎三價銅錯合物合成及其性質探討
Synthesis and Structure of Novel Copper(III) Complexes with a Supporting Polydentate Ligand of Tris(3-(trimethylsilyl)2-mercaptophenyl)phosphine and their Property Study
指導教授： 李位仁
學位類別： 碩士
Master
系所名稱： 化學系
Department of Chemistry
論文出版年： 2011
畢業學年度： 99
語文別： 中文
論文頁數： 66
中文關鍵詞： 銅三價 、四牙基 、磷硫多牙基 、金屬錯合物
論文種類： 學術論文
相關次數： 點閱：146  下載：1 
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    • 我們利用去質子化的三腳四牙配位基P(C6H3-3-SiMe3-2-SH)3 (PS3TMS)與CuCl2和PPNCl在乙腈與四氫呋喃混合溶劑下反應，會發生自身氧化還原反應得到[PPN][CuClPS3TMS] (1)和PPNCuCl2，利用通入氧氣來氧化正二價銅離子可提高錯合物1的產率。如果使用類似之去質子化配位基PS3進行反應，就沒有辦法觀察到正三價銅錯合物之產生。
    將錯合物1和NaOMe進行反應會得到Cu(NHPPh3)PS3TMS (3)，因此推測反應過程中可能是先經由β-hydride elimination生成[PPN] [CuHPS3TMS]的中間態，進而與[PPN]+反應生成NHPPh3並配位到正三價銅離子中心，才會得到錯合物3。為了證明此反應過程會經過[PPN][CuHPS3TMS]中間態，因此將錯合物1直接與KBEt3H反應，也成功地得到錯合物3。若將錯合物1的陽離子置換成[PPh4]+生成[PPh4] [CuClPS3TMS] (2)，再與KBEt3H反應，會得到K2[(CuPS3TMS)2] (4)和氫氣，這個結果告訴我們反應過程中可能生成[PPh4][CuHPS3TMS]。

    The tripodal tetradentate ligand P(C6H3-3-SiMe3-2-SH)3 (PS3TMSH3) was deprotonated by NaH, and further reacted with CuCl2 in CH3CN and THF. The disproportionation of CuCl2 was occurred to form [PPN][CuClPS3TMS] (1) and PPNCuCl2. The yield of complex 1 in previous reaction could be improved by using dry O2 to oxidize Cu(II) ion. A similar ligand, P(C6H4- 2-SH)3 (PS3H3) was also employed to reacted with CuCl2. However, no CuIII complex was observed.
    Reaction of 1 with NaOMe afforded complex, [Cu(NHPPh3)PS3TMS] (3). This results suggested that an intermediates, [PPN][CuHPS3TMS], was generated through β-hydride elimination. The hydride attacted the cation, [PPN]+, to form NHPPh3, which coordinated to the CuIII center. To prove the formation of the [PPN][CuHPS3TMS] intermediates, complex 1 was reacted with KBEt3H to afford complex 3. If the counter ion of 1 changed to [PPh4]+ to form [PPh4][CuClPS3TMS] (2). Reaction of 2 with KBEt3H gave a new dinuclear complex, K2[(CuPS3TMS)2] (4) and H2 suggesting the possibility of [PPh4][CuHPS3TMS] formation.

    中文摘要…………………………………………………………………Ⅰ 英文摘要…………………………………………………………………Ⅱ 圖索引……………………………………………………………………Ⅲ 表索引……………………………………………………………........…Ⅶ 附錄索引………………………………………………………………....Ⅷ 第一章 緒論 1-1前言 1 1-2文獻上PS3TMS錯合物介紹及應用 6 1-3文獻上常見的Cu(III)錯合物介紹 11 1-4研究方向 16 第二章 實驗部分 2-1一般實驗……………………………………………………………17 2-2儀器…………………………………………………………………18 2-3溶劑…………………………………………………………………20 2-4藥品…………………………………………………………………22 2-5配位基的合成與鑑定………………………………………………23 2-5.1 PS3TMS: Tris(3-(trimethylsilyl)2-mercaptophenyl)phosphine…… 23 2-5.2 PS3: tris(2-mercaptophenyl)phosphine的合成與鑑定.………… 28 2-6化合物的合成與鑑定………………………………………………29 2-6.1合成[PPN][CuClPS3TMS ] (1) ……………..........................…...…29 2-6.2合成[PPh4][CuClPS3TMS] (2)...........................................................31 2-6.3合成[Cu(NHPPh3)PS3TMS] (3).........................................................32 2-6.4合成K2[(CuPS3TMS)2] (4)................................................................33 第三章 結果與討論 3-1配位基的合成探討…………………………………………………35 3-2錯合物的結果探討…………………………………………………38 3-2.1 [PPN][CuClPS3TMS ] (1) 的合成、結構及性質分析……………………………………....38 3-2.2 [PPh4][CuClPS3TMS] (2) 的合成、結構及性質分析……………………….……………….44 3-2.3[Cu(NHPPh3)PS3TMS] (3) 的合成、結構、性質及光譜分析……………………………..…46 3-2.4 K2[(CuPS3TMS)2] (4) 的合成、結構、性質及光譜分析……………………………......49 3-2.5錯合物1與NaOMe反應探討比較……………………..………52 3-2.6錯合物1與KBEt3H反應探討比較......................................……54 3-2.7錯合物2與KBEt3H反應探討比較……................................…..58 3-3錯合物的晶體結構解析.................................................................... 61 第四章 結論與展望 參考文獻 ....................................................................................................65 附錄

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