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

Synthesis,structure and electrochemistry of Pd and Pt complexes with bis(fluoro-ponytailed)bipyridine ligands

侯曦鈞(Hsi-Chun Hou)

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(2008年)

https://doi.org/10.6841/NTUT.2008.00338

摘要

本氟素高科技研究室，已合成出一系列於聯吡啶的4,4′位置有兩個全氟化烷基側鏈之聯吡啶螯合劑 [4,4′-bis(RfCH2OCH2)-2,2′-bipyridine] (Rf = C3F7 , HC4F8, etc.)，利用親核取代步驟，[4,4′-bis(bromomethyl)-2,2′-bipyridine]與一系列氟醇鈉反應，可生成氟化烷基側鏈的聯吡啶配位基，產率極高。產物再用昇華方式加以純化後，以NMR、GC/MS、FTIR加以確認。
螯合劑隨後再與MCl2(CH3CN)2反應[M=Pd、Pt] ,生成聯吡啶鈀及鉑錯合物，並用NMR、FAB、FTIR 加以鑑定。我們將其中氟素較低的鈀錯合物成功地再結晶後，選取較佳的單晶，測取X-ray繞射數據，並鑑定其晶體之結構。
合成一系列鈀、鉑錯合物之外，我們也對之進行電化學(Cyclic Voltammetry, CV)之量測，以討論其電化學性質。

關鍵字

含氟鏈吡啶螯合劑(錯合物 ； 結晶 ； 電化學

並列摘要

As part of the on-going program in the high-tech flourine research laboratory, we have synthesized a series of bipyridine ligands which have two perfluoroalkylated chains each at the 4,4′ positions of
[4,4′-bis(RfCH2OCH2)-2,2′-bipyridine] (Rf = C3F7, HC4F8 , etc.). By the mechanism of nucleophilic substitution reactions, the [4,4′-bis(bromomethyl)-2,2′
bipyridine] undergoes a chemical reaction with the fluoroue alkoxide of various chain length synthesized in our laboratory, to produce fluoroalkylated bipyridine ligand. The yield is quite high. The fluoroalkylated bpy ligands are purified by simple sublimation. The synthesized bpy ligands are characterized by the NMR, GC/MS, and FTIR methods. The synthesyed bpy ligands then go through a chemical reaction with MCl2(CH3CN)2 [M = Pd、Pt] to form the Pd and Pt complexes, which are verified by using NMR, FAB, or FTIR methods. Both Pd and Pt complexes with lower fluorine contents have been recrystallized for single-crystals of better quality, which have been studied by X-ray diffraction to reseal the mole under structure.
Furthermore，the CV (Cyclic Voltammetry) of the resulting Pd and Pt complexes have been measured to characterize electrochemical property of the complexs.

並列關鍵字

bipyridine ligands ； complexes ； recrystallized ； electrochemical

參考文獻

[1] L. Rosenberg, D. N. Kobus, J.Organomet. Chem. 2003, 685,107-112

[10]N. Lu, Y-C Lin, Tetrahedron Lett. 2007, 48, 8823–8828

Yellowlees, J. Chem. Soc., Dalton Trans., 1999, 4203–4208

[14]P. S. Braterman, J.I . Song, J. Org. Chem, 1991, 56, 4678-4682

Electrochem 2005, 9, 764–777