首页> 美国卫生研究院文献>Biochemical Journal >Formation of aryl and aryldiazenyl complexes in reactions of arylhydrazines and aryldiazenes with a synthetic model compound of haemoprotein.
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Formation of aryl and aryldiazenyl complexes in reactions of arylhydrazines and aryldiazenes with a synthetic model compound of haemoprotein.

机译:在芳基肼和芳基二氮烯与血红蛋白合成模型化合物反应中形成芳基和芳基二氮烯基络合物。

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摘要

The anaerobic reaction of chelated protohaemin, a synthetic model compound of ferrihaemoglobin, with phenyldiazene produced a compound with the visible-absorption spectrum of a ferrihaemochrome. The compound reacted with CN-, which is a ligand of both ferric and ferrous porphyrins, to produce the complex of the synthetic ferrihaemoglobin with CN-. Though the spectrum of the compound formed by the addition of phenyldiazene to chelated protohaemin is characteristic of a ferric porphyrin complex, this compound reacted with both toluene-p-sulphonylmethyl isocyanide and CO, which are strong ligands of ferrous porphyrins, to produce the corresponding ferrous complexes. These ligand-binding reactions indicated that the complex of chelated protohaem with phenyldiazene can behave either as a complex of a ferric porphyrin with phenyldiazenyl anion (C6H5N = N-) or a complex of a ferrous porphyrin with phenyldiazenyl radical (C6H5N = N.). Para substituents on phenyldiazene were without effect on the formation of 4-substituted phenyldiazenyl complexes with chelated protohaem. Ortho substituents resulted in less-stable complexes. The phenyl complex of chelated protohaem was prepared by the aerobic reaction of phenylhydrazine with chelated protohaemin, and its structure was confirmed by its n.m.r. spectrum. The ligand-binding properties, n.m.r. spectrum and absorption spectrum of this complex differed from those of the phenyldiazenyl complex. The phenyl complex also was produced when the phenyldiazenyl complex was exposed to O2.
机译:螯合的原血红素(一种亚铁血红蛋白的合成模型化合物)与苯基二氮烯的厌氧反应产生了一种具有亚铁血红色素的可见吸收光谱的化合物。该化合物与作为铁和亚铁卟啉的配体的CN-反应,生成合成的亚铁血红蛋白与CN-的复合物。尽管通过将苯基二氮烯添加到螯合的原血红素中形成的化合物的光谱是三价铁卟啉配合物的特征,但该化合物与甲苯-对-磺酰甲基异氰酸酯和CO(铁卟啉亚铁的强配体)反应生成相应的亚铁。复合体。这些配体结合反应表明,螯合原虫与苯基二氮烯的络合物可以表现为铁卟啉与苯基二氮烯基阴离子的络合物(C6H5N = N-),也可以表现为亚铁卟啉与苯基二氮烯基的络合物(C6H5N = N.)。苯基二氮烯上的对位取代基对形成具有螯合原血红素的4-取代的苯基二氮烯基配合物没有影响。邻位取代基导致稳定性较差。通过苯肼与螯合的原血红素的需氧反应制备了螯合的原血红素的苯基配合物,并通过其n.m.r.确定了其结构。光谱。配体结合性能,n.m.r。该配合物的光谱和吸收光谱不同于苯基二氮烯基配合物的光谱和吸收光谱。当苯基二氮烯基络合物暴露于O2时,也会生成苯基络合物。

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