中文摘要
本篇論文研究釕的β-二酮亞胺以及β-酮亞胺等錯合物對於一氧化氮反應性的研究，希望可以了解一氧化氮還原成胺類過程中的反應機制。在室溫條件下，釕二價金屬β-酮亞胺錯合物Ru(Nacac)Dipp(Cl)(η6-p-cymene) (1) ((Nacac)Dipp = OC(Me)CHC(Me)NC6H3iPr2)與過量的一氧化氮進行反應，經由鑑定其產物得知一氧化氮與配基酮亞胺骨架上的碳鍵結，產生一個新的配基並形成了一個新穎的化合物Ru[κ2-ONCC(O)MeC(Me)N-2,6-iPr2C6H3](Cl)(η6-p-cymene) (2)。
以β-二酮亞胺作為配基的釕金屬錯合物，Ru(Nacnac)Dep(Cl)(η6-p-cymene) (3) ((Nacnac)Dep = CH(C(Me)NC6H3Et2)2)、Ru(Nacnac)Dep(η6-p-cymene) (5)等錯合物與過量一氧化氮反應及其衍生物的研究。錯合物3與過量的一氧化氮進行反應可以得到Ru(Nacnac)Dep(NO)Cl2 (4)，而錯合物5與一當量的一氧化氮反應可得產物為一個釕金屬配位有一個亞硝基的錯合物 [(μ-NO)[Ru(Nacnac)Dep]2 (6)，當錯合物5與過量的一氧化氮反應，則可收集到化合物(μ-κ2:κ2-NO)(μ-OH)[Ru(Nacnac)Dep(NO)]2 (7)，再將錯合物7與鉀石墨進行反應，還原可得單核帶負一價的釕二亞硝基錯合物{[K(18-crown-6)][Ru(Nacnac)Dep(NO)2]} (8)，將錯合物8與2,6-二甲基吡啶‧硼氟酸反應，可分離出兩個產物，一個為有次硝酸配位在釕金屬上的雙釕錯合物{[μ-κ1:κ1-N(H)O:η2-N(H)O][Ru(Nacnac)Dep(NO)]}2 (9)，另一個為有羥基和胺基配位在釕金屬上的雙釕金屬錯合物，{[μ-κ1:κ1-NH][Ru(Nacnac)Dep(NO)(OH)]}2 (10)。
此外我們將錯合物3與錯合物5混合後與過量的一氧化氮反應可得Ru(Nacnac)Dep(NO)2(Cl) (11)。

Abstract
In this thesis, we studied the possible mechanism of NO reductase. By simplifying the conditions, we used β-diketiminate and β-ketoiminate as ligands to stabilize ruthenium complexes.
We first synthesized the divalent complex Ru(Nacac)Dipp(Cl)(η6-p-cymene) (1) ((Nacac)Dipp = OC(Me)CHC(Me)N-2,6-iPr2C6H3) as a starting reactant to react with an excess amount of nitric oxide (NO), from which we obtained the complex Ru[κ2-ONCC(O)MeC(Me)N-2,6-iPr2C6H3](Cl)(η6-p-cymene) (2). In 2, a new ligand was formed from the attack of NO to the backbone of Nacac.
We then studied the reactivity of β-diketiminate-supported ruthenium complexes. We prepared two compounds Ru(Nacnac)Dep(Cl)(η6-p-cymene) (3) ((Nacnac)Dep = CH(C(Me)NC6H3Et2)2) and Ru(Nacnac)Dep(η6-p-cymene) (5) and allowed them to react with excess amouns of NO. Complex 3 reacted with an excess amount of NO, from which the mononitrosyl ruthenium complex Ru(Nacnac)Dep(NO)Cl2 (4) was obtained. On the other hand, the reaction of 5 with one equivalent of NO led to the isolation of a binuclear complex, which has two bridging nitrosyl groups between two ruthenium, [(μ-NO)[Ru(Nacnac)Dep]2 (6). When 6 was reacted with one more equivalent of NO, the dinuclear complex (μ-κ2:κ2-NO)(μ-OH)[Ru(Nacnac)Dep(NO)]2 (7) was obtained, which features a side-on bound nitrosyl ligand. Subsequent KC8 reduction of 7 resulted in the formation of the mononuclear compound {[K(18-crown-6)][Ru(Nacnac)Dep(NO)2]} (8). Upon treatment of complex 8 with 2,6-dimethylpyridinium tetrafluoroborate, two unique compounds {[μ-κ1:κ1-N(H)O:η2-N(H)O][Ru(Nacnac)Dep(NO)]}2 (9), which consists of two hypernitrious acids as ligands bridging two ruthenium atoms and {[μ-κ1:κ1-NH][Ru(Nacnac)Dep(NO)(OH)]}2 (10) with two bridging imido and two terminal hydroxyl groups were isolated.
Exposure of a mixture of 3 and 5 to an excess amouns of NO, the dinitrosyl complex Ru(Nacnac)Dep(NO)2(Cl)(11) was obtained.

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