中性{Fe(NO)₂}₉二亚硝酰基铁配合物（DNIC）[(SC₆H₄ - o - NHCOPh)(Im)Fe(NO)₂]（Im = 咪唑）：阴离子/中性{Fe(NO)₂}₉ DNICs与鲁辛红酯之间的相互转化
Neutral {Fe(NO)2}9 dinitrosyliron complex (DNIC) [(SC6H4-o-NHCOPh)(Im)Fe(NO)2] (Im = imidazole): interconversion among the anionic/neutral {Fe(NO)2}9 DNICs and Roussin's red ester.
作者信息
Tsai Ming-Li, Liaw Wen-Feng
机构信息
Department of Chemistry, National Tsing Hua University, Hsinchu 30013, Taiwan.
出版信息
Inorg Chem. 2006 Aug 21;45(17):6583-5. doi: 10.1021/ic0608849.
A neutral {Fe(NO)2}9 dinitrosyliron complex (DNIC) [(SC6H4-o-NHCOPh)(Im)Fe(NO)2] (Im = imidazole; 2) was prepared by the reaction of [Fe(mu-SC6H4-o-NHCOPh)(NO)2]2 (1) and 2 equiv of imidazole. In the synthesis of the anionic {Fe(NO)2}9 DNIC [(SC6H4-o-NHCOPh)2Fe(NO)2]- (3), thiolate [SC6H4-o-NHCOPh]- triggers ligand substitution of DNIC 2 to yield DNIC 3. At 298 K, complexes 2 and 3 exhibit well-resolved nine- and five-line electron paramagnetic resonance (EPR) signals at g = 2.031 and 2.029, respectively, the characteristic g value of DNICs. The facile interconversions among the neutral {Fe(NO)2}9 complex 2, the anionic {Fe(NO)2}9 complex 3, and Roussin's red ester 1 were demonstrated. The EPR spectrum (the pattern of hyperfine splitting) in combination with the IR nu(NO) (the relative position of the nu(NO) stretching frequencies) spectrum may serve as an efficient tool for the discrimination of the anionic {Fe(NO)2}9 DNICs, the neutral {Fe(NO)2}9 DNICs, and Roussin's red ester.
通过[Fe(μ-SC6H4-o-NHCOPh)(NO)2]2（1）与2当量咪唑反应制备了中性{Fe(NO)2}9二亚硝酰基铁配合物（DNIC）[(SC6H4-o-NHCOPh)(Im)Fe(NO)2]（Im = 咪唑；2）。在合成阴离子型{Fe(NO)2}9 DNIC [(SC6H4-o-NHCOPh)2Fe(NO)2]-（3）时，硫醇盐[SC6H4-o-NHCOPh]-引发DNIC 2的配体取代反应生成DNIC 3。在298 K下，配合物2和3分别在g = 2.031和2.029处表现出分辨良好的九线和五线电子顺磁共振（EPR）信号，这是DNICs的特征g值。证明了中性{Fe(NO)2}9配合物2、阴离子型{Fe(NO)2}9配合物3和鲁辛红酯1之间的 facile 相互转化。结合红外ν(NO)（ν(NO)伸缩频率的相对位置）光谱的EPR光谱（超精细分裂模式）可作为区分阴离子型{Fe(NO)2}9 DNICs、中性{Fe(NO)2}9 DNICs和鲁辛红酯的有效工具。
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