Abstract
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.