(a) 含短氟聯吡啶及其鈀和鉑錯合物之研究 (b) 含氟鏈鈀錯合物嵌入ZrP運用在Sonogashira和Heck反應

(a) Studies of Pd and Pt complexes With Short Fluoro-ponytailed Bipyridine Ligands (b) ZrP-supported Palladium Complex Catalyzed Sonogashira and Heck reaction

卓均蔚(Chun-wei Cho)

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(2013年)

摘要

(a)
合成一系列含短氟聯吡啶[4,4’-bis(RfCH2OCH2)-2,2’-bipyridine和5,5’-bis(RfCH2OCH2)-2,2’-bipyridine，Rf= CF2（2F）、CF3（3F）、CF2CF2H（4F）、CF2CF3（5F）、(CF2)2CF3（7F）、(CF2)3CF2H（8F）]以及其溴化鈀、氯化鉑、溴化鉑和碘化鉑等錯合物。透過NMR（1H、13C、19F）、IR、高解析質譜儀（HR-FAB）、X-ray單晶繞射儀和熔點鑑定這些錯合物，將這些短氟鍊錯合物之性質進行比較。

(b)
將含短氟聯吡啶鈀錯合物嵌入至ZrP（Zirconium phosphate）製成一種可回收利用的新型觸媒並運用在Sonogashira催化反應。經過測試，該觸媒擁有不錯的催化性，但經歷數次的回收，催化性已降低。推測是錯合物溶解於溶劑而從ZrP脫離，使得回收得到的觸媒越來越少，降低反應率。

關鍵字

多氟聯吡啶螯合劑 ； 均相系列 ； 鈀 ； 鉑 ； 錯合物 ； X-射線衍射研究 ； 氫鍵 ； 觸媒回收 ； Sonogashira反應 ； Heck反應 ； 磷酸鋯 ； 異相催化

並列摘要

(a)
Synthesize a series of the small fluoro-ponytailed bipyride ligands [4,4’-bis(RfCH2OCH2)-2,2’-bipyridine and 5,5’-bis(RfCH2OCH2)-2,2’-bipyridine，Rf= CF2（2F）, CF3（3F）, CF2CF2H（4F）, CF2CF3（5F）, (CF2)2CF3（7F）, (CF2)3CF2H（8F）] amd their complexes（These ligands react with PdBr2, PtCl2, PtBr2 and PtI2） These complexes have been characterized by NMR（1H, 13C, 19F）, IR, High-resolution mass spectrum（HR-FAB）, X-ray diffraction and melt point, then compared their characters each other.

(b)
The complexes intercalated ZrP（Zirconium phosphate）will make new recycling catalysts for the Sonogashira reaction. The catalysts have good catalytic effect in the test, but its effect will reduce after the recycle. We think that the complexes dissolve in the solvent, then desorb from ZrP. The catalysts are much less than before, reducing the reactive rate.

並列關鍵字

Polyfluorinated bipyridyl ligands ； Homogeneous series ； Palladium ； Platinum ； Complex ； X-ray diffraction studies ； Hydrogen bondings ； Catalyst recycling ； Sonogashira reaction ； Heck reaction ； Alpha Zirconium Phosphate ； Heterogeneous Catalysis

參考文獻

[20] 侯曦鈞，特殊含氟鏈聯吡啶鈀及鉑錯合物的合成、結構及電化學研究，碩士論文，國立台北科技大學有機高分子所，臺北，2008

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