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Bioinspired oxidation of oximes to nitric oxide with dioxygen by a nonheme iron(II) complex
JBIC Journal of Biological Inorganic Chemistry ( IF 3 ) Pub Date : 2019-10-21 , DOI: 10.1007/s00775-019-01726-6
Shrabanti Bhattacharya , Triloke Ranjan Lakshman , Subhankar Sutradhar , Chandan Kumar Tiwari , Tapan Kanti Paine

The ability of two iron(II) complexes, [(TpPh2)FeII(benzilate)] (1) and [(TpPh2)(FeII)2(NPP)3] (2) (TpPh2 = hydrotris(3,5-diphenylpyrazol-1-yl)borate, NPP-H = α-isonitrosopropiophenone), of a monoanionic facial N3 ligand in the O2-dependent oxidation of oximes is reported. The mononuclear complex 1 reacts with dioxygen to decarboxylate the iron-coordinated benzilate. The oximate-bridged dinuclear complex (2), which contains a high-spin (TpPh2)FeII unit and a low-spin iron(II)–oximate unit, activates dioxygen at the high-spin iron(II) center. Both the complexes exhibit the oxidative transformation of oximes to the corresponding carbonyl compounds with the incorporation of one oxygen atom from dioxygen. In the oxidation process, the oxime units are converted to nitric oxide (NO) or nitroxyl (HNO). The iron(II)–benzilate complex (1) reacts with oximes to afford HNO, whereas the iron(II)–oximate complex (2) generates NO. The results described here suggest that the oxidative transformation of oximes to NO/HNO follows different pathways depending upon the nature of co-ligand/reductant.Graphic abstract


中文翻译:

非血红素铁(II)配合物通过生物启发将肟肟氧化为一氧化二氮。

[[Tp Ph2)Fe II(苯甲酸盐)](1)和[[Tp Ph2)(Fe II2(NPP)3 ](2)(Tp Ph2  = hydrotris(3)据报道,在肟的O 2依赖性氧化中,单阴离子的面部N3配体具有1,5-二苯基吡唑-1-基)硼酸酯(NPP-H =α-异亚硝基苯乙酮)。单核络合物1与双氧反应以使铁配位的苯甲酸酯脱羧。肟酸桥联的双核配合物(2),其中包含高自旋(Tp Ph2)Fe II单元和低旋铁(II)-肟酸单元在高旋铁(II)中心激活双氧。两种配合物均表现出肟的氧化转化为相应的羰基化合物,同时从双氧中引入一个氧原子。在氧化过程中,肟单元被转化为一氧化氮(NO)或硝氧基(HNO)。铁(II)-苯甲酸酯络合物(1)与肟反应生成HNO,而铁(II)-肟酸络合物(2)生成NO。此处描述的结果表明,肟酸向NO / HNO的氧化转化取决于共配体/还原剂的性质遵循不同的途径。
更新日期:2019-10-21
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