雙亞硝基鐵化合物與氮雜環碳烯(NHCs)及鹵素、氰酸根、硫氰酸根配位基的合成與性質鑑定

雙亞硝基鐵化合物(DNIC)在生物體之主要功能為傳遞與儲存一氧化氮的功能備受矚目。本論文透過置換配位基合成類似生物體的雙亞硝基鐵化合物，並以含氮異環碳烯N-Heterocyclic Carbenes(NHC)為配位基合成一系列雙亞硝基鐵化合物。第一部分利用先前的文獻[1]的 [iMes-Fe(NO)3][BF4] (4)與含鹵素鹽類(如:PPh4Cl、KBr、KI)在THF反應下得到雙亞硝基鐵錯合物iMes-Fe(NO)2Cl (5)、iMes-Fe(NO)2Br (6)、iMes-Fe(NO)2I (7)。在透過紅外線光譜儀分析後發現錯合物5、6與7在NO訊號位置排列順序與理論上並不相符合，理論上配體的σ-donating能力越強，中心金屬電子密度增加，π-backbonding變強，紅外線光譜會紅移，但實驗結果與理論不符合。本實驗試圖利用X-ray單晶繞射儀、UV、CV等儀器去說明其原因。第二部分利用[iMes-Fe(NO)3][BF4]與KOCN、KSCN在THF反應下得到中性{Fe(NO)2}9雙亞硝基鐵錯合iMes-Fe(NO)2(OCN) (9)、iMes-Fe(NO)2(SCN) (8)化合物，本實驗透過紅外線光譜和X-ray單晶繞射儀鑑定其結構及電化學分析去探討氧化還原活性。

關鍵字

雙亞硝基鐵化合物；亞硝基； DNIC ；含氮異環碳烯

並列摘要

The main function of dinitrosyl iron complexes (DNICs) in the organism is to transfer and storage nitric oxide. We synthesized the dinitrosyl iron complexes by replacing ligands with N-Heterocyclic Carbenes(NHCs) ligand to form a series of complexes in this thesis. First part, in the literature reviews, we found that reaction of iMes-Fe(NO)3[BF]4 (4) and hailed (for example: PPh4、KBr、KI) under THF solvent condition leads to the formation of dinitrosyl iorn complexes (5) iMes-Fe(NO)2Cl (6) iMes-Fe(NO)2Br (7) iMes-Fe(NO)2I. Complexes 5、6 and 7 FT-IR(NO) signals position order do not measure up to the the theoretical values. In theory, the stronger σ–donating cause ligands, the stronger central metals electron density and π–backbonding behavior, also the IR signals in FTIR will drift to the redshift. We characterized complexes 5、6 and7 by X-ray single crystal diffraction, UV-vis and CV(Cyclic Voltammetry) to figure out the reasons of why the experimental results don’t match the theoretical values. Second part, reaction of[ iMes-Fe(NO)3][BF4] and KOCN, KSCN respectively under THF solvent reaction condition result in the formation of neutral dinitrosyl iron complexes iMes-Fe(NO)2(OCN) (9) and iMes-Fe(NO)2(SCN) (8). We characterized these complexes by X-ray and analyzed it’s redox behavior by the electrochemistry.