含硫及二醯胺大環與鈀（II）錯合物的性質研究

Characterization of the Complexes of Pd(II) of Macrocyclic Diamides Containing Sulfur

陳恒毅(Heng Yi Chen)

指導教授 ： 劉高家秀

國立臺灣師範大學/理學院/化學系/碩士(1999年)

摘要

本研究以Hruby 和Stock 的醯胺合成法合成一系列不同環數含硫及二醯胺大環冠狀化合物，利用萃取及傳輸實驗來探討對過渡金屬Pd（II）的錯合及傳輸能力，並求得較佳的萃取傳輸條件。對於萃取結果很好但傳輸能力卻不好的現象，可由配位子和Pd（II）錯合的結構來說明。
由結果發現，將萃取的方式由旋轉﹙stir﹚改為震盪﹙shake﹚ ，可將萃取平衡時間由210分鐘縮短至15分鐘，節省了很多時間，並且提昇萃取效率。另外，配位子的結構中在二醯胺間為4個碳（3c，4c，5c），與Pd（II）錯合則主要形成out 形式。傳輸實驗中，配製Pd（II）時加的鹽酸愈少，則傳輸速率愈好。
我們分別以紫外/可見光光譜儀的莫耳分率法和電位滴定法（potentiometric titration method）求得配位子和Pd（II）在甲醇中有加鹽酸和不加鹽酸的穩定常數（Ks）。
我們在不同實驗條件下，得到4a-in，4a-out，3b-out 的單晶，經X-ray 繞射鑑定，在中性條件下得到黃色的4a-in晶體，醯胺基去質子化配位至鈀上；在酸性條件下得到橘紅色的4a-out，3b-out晶體，發現只有硫配位到鈀上，而醯胺基並不會去質子化和鈀產生配位。

關鍵字

大環冠狀化合物 ； 鈀 ； 萃取 ； 傳輸 ； 穩定常數 ； 莫耳分率法 ； 電位滴定法

並列摘要

Several macrocyclic diamides containing sulfur of various ring sizes were synthesized by modified Hruby and Stocks amide synthesis. They have been used to study the ability of complexation with palladium ion using techniques such as solvent extraction and liquid membrane transport. Results where solvent extraction are good, but liquid membrane transport results are bad are explained by the differences in complex structures.
The extraction time can be greatly reduced when stirring is replaced by shaking. Results obtained by shaking 15 min are better or equivalent to those by stirring 210 min at 300 r.p.m. Ligands which have 4 carbons between the two amide groups complexed with Pd（II） in the Pd (II)out-forms.
We determine the stability constants（logKs）by using mole-ratio method of UV/Vis spectrometry to complexes of ligands and Pd（II）with hydrochloric acid , and potentiometric titration method to determine the stability constants（logKs） the complexes of Pd（II）with ligands without hydrochloric acid.
Two kind of single crystal of the metal-macrocyclic diamide complexes have been obtained and analyzed by single crystal X-ray diffraction. The yellow 4a-in obtained under neutral condition is a tetracoordinated. In which the sulfur and nitrogen atoms in the macrocyclic diamide ring are all coordinated with the Pd (II) ion; due to the deprotonation of the hydrogen on amide group.The red-orange crystal of 4a-out, 3b-out obtained under acidic condition is also a tetracoordinated. In which only the sulfur atoms of the macrocyclic diamide ring are coordinated with the Pd(II) ion.

並列關鍵字

macrocyclic ； palladium ； extraction ； transport ； stability constant ； mole-ratio method ； potentiometric titration method

參考文獻

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