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  • 學位論文

新穎多牙氮配位基合成及其單核與雙核釕金屬錯合物之合成與催化探討

Synthesis of the Novel Multidentate Ligand and Its Mono- and Di-nuclear Ruthenium Complex for Cyanation of Tertiary Amines

指導教授 : 劉緒宗

摘要


本篇論文的主要內容為合成2,8-di(2-pyridyl)-5-phenyl-l,9,10-anthyridine (4a)多牙氮配位基以及其單核和雙核釕金屬錯合物,並將其作為三級胺氫化反應的催化劑,進而比較單核與雙核釕金屬錯合物之性質與催化活性。 將2,6-diamino-4-phenylpyridine-3,5-dicarboxaldehyde (3)與2-acetylpyridine進行Friedlander synthesis,可合成擁有五個N配位基團的化合物4a,擁有比bpNP更多的配位環境以及立體空間。使用兩種釕金屬前趨物RuCl2(CO)3(THF)以及[(η6-p-cymene)RuCl2]2與4a進行配位可分別得到單核釕金屬錯合物Ru1 ([(4a)Ru(CO)3Cl)(Ru(Cl)3(CO)3])以及雙核釕金屬錯合物Ru2 ([(4a)Ru2(p-cymene)2(Cl)2][(PF6)(Cl)]);藉由X光單晶繞射分析儀器鑑定,顯示此系列釕金屬錯合物均為六配位的形態存在,同時利用NMR以及ESI-MASS質譜分析兩錯合物的結構,其數據皆與晶體資料相符合。多種數據顯示Ru2上其中一個p-cymene擁有fluxion的現象,可能是p-cymene以垂直其C2軸垂直並通過苯環某一組對稱的碳做為軸,進行振動的現象。利用變溫1H NMR實驗觀察p-cymene隨溫度降低之氫譜變化並計算出此旋轉的轉動速率以及自由能。 在催化應用探討上,測試單釕金屬錯合物Ru1以及雙釕金屬錯合物Ru2對於三級胺氰化反應的活性。發現酸性條件下,錯合物Ru2在雙氧水做氧化劑下,可有效將氰化鈉與三級胺反應,得到產率不錯的α-胺基腈產物。相較於單金屬錯合物Ru1,雙金屬錯合物Ru2為較佳的催化濟。

並列摘要


We have successfully prepared 2,8-di(2-pyridyl)-5-phenyl-l,9,10-anthyridine (4a), which is a multidentate ligand. For the ligand synthesis, the double Friedlander condensations of 2,6-diamino-4-phenylpyridine-3,5-dicarboxaldehyde (3) with 2-acetylpyridine yielded 4a. Coordination of 4a with two kinds of ruthenium precursor, RuCl2(CO)3(THF) and [(η6-p-cymene)RuCl2]2 , resulted in the formatioon of a mono-nuclearspecies ([(4a)Ru(CO)3Cl)(Ru(Cl)3(CO)3]) (Ru1) and a dinuclear ruthenium complex ([(4a)Ru2(p-cymene)2(Cl)2][(PF6)(Cl)]) (Ru2), respectively. Two complexes were characterized by X-ray crystals, NMR, ESI-MASS. We had found that one of the p-cymene of Ru2 is fluxional, and we proposed that the p-cymene might vibrate when Ru2 is dissolved in solvent. The vibrate frequency and free energy was determined by the low-temperature 1H NMR experiment. In the catalytic application, mono- and di-nuclear ruthenium complexes were active for the cyanation of tertiary amines with sodium cyanide. Complex Ru2 afforded the corresponding a-aminonitriles with good yields with hydrogen peroxide as the oxidant under acidic condition.

參考文獻


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被引用紀錄


黃大維(2016)。萘啶配基之雙金屬錯合物的合成、性質與催化活性〔博士論文,國立臺灣大學〕。華藝線上圖書館。https://doi.org/10.6342%2fNTU201610053
鄧運楨(2013)。多牙氮配位基之釕與銅錯合物之合成與催化探討〔碩士論文,國立臺灣大學〕。華藝線上圖書館。https://doi.org/10.6342%2fNTU.2013.00876

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