透過您的圖書館登入
IP:18.119.121.101
  • 學位論文

四價錳錯合物之逐步還原與反應性之探討

Stepwise Reduction and Reactivity of Manganese(IV) Complexes

指導教授 : 李位仁
若您是本文的作者,可授權文章由華藝線上圖書館中協助推廣。

摘要


本研究延續先前本實驗室任少緯學長之論文,以兩分子含磷硫 之三牙配位基H2PS2與製備出錳錯合物MnIV(PS2)2,於室溫及空氣下穩定之四價錳錯合物,以CV電化學確定其可能存三價、二價之氧化態,並藉由還原劑CoCp2、KC8等,分別獲得二價三價之錳錯合物[MnIII(PS2)2]─ 、[MnII(PS2)2]2─ 晶體,以X-ray單晶繞射獲得其結構,並針對其不同的電子組態進行EPR、SQUID、NMR-Evans Methods鑑定。並且發現了錳三價錯合物中之硫醇基(Thiolate)配位基具有顯著的親核性質,因此以親電試劑(CH3)3OBF4作為甲基提供試劑,實現了硫醇基烷化的反應並獲得其結構[MnIII(PS2)(PSS-CH3)],此反應於前週期過渡金屬是並不常見的,此結構也證實了[MnIII(PS2)2]錯合物所具有的反應潛力,未來希望能透過不同的烷基加成修飾,來達到活化此系列錯合物的效果。

並列摘要


This study was continued from the previous works in our groups. The manganese (IV) complex MnIV(PS2)2 which is stable under air and room temperature was synthesized by the dithiolate-phousphine tridentate ligands H2PS2. Cyclic voltammetry revealed the probability oxidation state of Mn(III) / Mn(II) are existing. The [MnIII(PS2)2] / [MnII(PS2)2] complex was reduced by CoCp2 / KC8. The molecular structure CoCp2[MnIII(PS2)2] and Na2[MnII(PS2)2] was acquired from the X-ray diffraction. The EPR, SQUID, NMR-Evans methods were used for the identification of their electron configuration. Furthermore, The significant nucleophilicity was found with the thiolate ligand of the [MnIII(PS2)2]. Therefore the electrophilic reagent (CH3)3OBF4 was used as a reagent for providing the methyl cation (Me+). The thiolate-alkylation was successful and the single crystal [MnIII(PS2)(PSS-CH3)] was obtained and the thiolate-alkylation with complex is not common early-transition metals. The result shows the potential for activating these series of complex through different alkyl addition.

參考文獻


1-1. Jørgensen,C.K. Coord. Chem. Rev. 1966, 1, 164
1-2. 劉玉嬌,江明錫,黃意嵐,化學, 2014,72(2) ,67-76 Doi:10.6623/chem.2014009
1-3. Jessica D .Gardner, Thomas C. Brunold* Biochemistry,2010, 49, 6033–6041
1-4. Devesh Kumar* ,Walter Thiel, and Sam P. de Visser*,.J. Am. Chem. Soc 2011, 133, 3869–3882
1-5. Brian M. Barry, Benjamin W. Stein, and Richard A. Kemp* Inorg. Chem. 2013, 52, 9875−9884

延伸閱讀