(a) 可回收利用之陽離子型含氟鏈鈀觸媒在Sonogashira催化反應上的應用 (b) 含短氟鏈聯吡啶金屬錯合物之合成與鑑定

(a) Cationic Palladium Complex-catalyzed Sonogashira reaction under Thermomorphic mode (b) Synthesis, Struture of Metal Complexes with Bis(short fluoro-ponytailed) Bipyridine Ligand

吳仲偉(Zong-Wei Wu)

指導教授 ： 呂良賜

國立臺北科技大學/工程學院/有機高分子研究所/碩士(2010年)

摘要

(a) 可回收利用之陽離子型含氟鏈鈀觸媒在Sonogashira催化反應上的應用

本人利用本實驗室自行合成之陽離子型含氟鏈(η3-丙烯基)鈀錯合物，其通式為[Pd(η3-allyl)(4,4’-bis-(RfCH2OCH2)-2,2’-bpy)]OTf (錯合物1a, Rf = C10F21)，進行Sonogashira催化反應。利用含長氟鏈金屬錯合物對DMF具有溫控及雙相系統催化的特性，在此研究中，我們根據此特性，進行一系列催化反應。其中，以芳香基碘化物及溴化物來與苯乙炔在DMF中以140 ± 5℃下進行不含銅的Sonogashira反應，發現以4-nitro-iodobezene為起始物，在溫控條件下可重複反應5次；在FBS條件下皆可重複3次以上，而還具有好的催化活性。

(b) 含短氟鏈聯吡啶金屬錯合物之合成與鑑定

本人已成功合成並純化[4,4’-bis-(RfCH2OCH2)-2,2’-bpy)，Rf = CF3、C2F5](聯吡啶螯合劑3、5F-lig)。利用此2種螯合劑與鈀、鉑、釕等3種金屬化合物作鍵結，得到目標的含短氟鏈聯吡啶金屬錯合物，並以NMR (1H，19F與13C)、FTIR、高解析質譜儀(HR-FAB)、X-ray單晶繞射儀進行鑑定。其中釕金屬錯合物：CT5、CT5-HTBA應用在太陽能電池研究上，並對其光電性質作探討。

關鍵字

鈀催化耦合反應 ； 染料敏化太陽能電池

並列摘要

(a) Cationic Palladium Complex-catalyzed Sonogashira reaction under Thermomorphic mode

We used our self-synthesized novel cationic (η3-Allyl) palladium complexe: [Pd(η3-allyl)(4,4’-bis-(RfCH2OCH2)-2,2’-bpy)]OTf (complex 1a, Rf = C10F21) to process the Sonogashira cross-coupling reaction. Metal complex with long fluoro-ponytailed chain has thermomorphic and FBS properties. By taking advantage of these two properties, we processed series catalytic reactions. We used aryl-iodide(bromide) as substrates to process the Cu-free Sonogashira cross-coupling reaction with phenylacetylene in DMF at 140 ± 5℃. The Pd catalysts easily recovered and reused up to 5 cycles in thermomorphic mode and up to 3 cycles in FBS mode with the uses of 4-nitro-iodobezene as the substrate.

(b) Synthesis, Struture of Metal Complexes with Bis(short fluoro-ponytailed)
Bipyridine Ligand

We had successfully synthesized and purified two bipyridine ligands : [4,4’-bis-(RfCH2OCH2)-2,2’-bpy)，Rf = CF3, C2F5] (abbr. 3, 5F-lig). The synthesized two bipyridine ligands then went through chemical reactions with MCl2(CH3CN)2[M=Pd、Pt]、dichloro(p-cymene)-ruthenium(II) to form Pd、Pt、Ru complexes. These complexes have been fully characterized by NMR (1H, 19F and 13C)、FTIR、high-resolution mass spectrum (HR-FAB)、X-ray diffraction. Finally, the ruthenium complexes : CT5、CT5-HTBA had been studied in the field of solar cells.

並列關鍵字

Thermomorphic mode ； CT5

參考文獻

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