取代巯基三唑配体的双核亚硝基铁配合物在DMSO中转化的实验和量子化学研究

IF 1.7 4区化学 Q3 CHEMISTRY, MULTIDISCIPLINARY

Russian Chemical Bulletin Pub Date : 2025-01-14 DOI:10.1007/s11172-024-4454-9

E. A. Zagainova, O. V. Pokidova, N. S. Emel’yanova, N. A. Sanina

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引用次数: 0

摘要

研究了水不溶性双核亚硝基铁配合物[Fe2(SC2N3C6H4NO2)2(NO)4](1)在DMSO中的转化过程。紫外-可见分光光度法表明配合物1在溶液中分解。利用TDDFT方法计算了该配合物的紫外和可见光区理论电子能谱，并对配合物的分子轨道进行了分析。结果表明，由于Fe-NO基团的电子跃迁引起的吸收带消失与NO的给予有关。利用量子化学计算得到了配合物1在DMSO中分解的总能量图，并研究了配合物1的两种转化机制，一种是通过铁原子配位数增加到6，另一种是通过μ-SCN桥破坏Fe-S键。

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Experimental and quantum chemical study of transformations of a binuclear iron nitrosyl complex with a substituted mercaptotriazole ligand in DMSO

The process of transformation of the water-insoluble binuclear iron nitrosyl complex [Fe₂(SC₂N₃C₆H₄NO₂)₂(NO)₄] (1) in DMSO was studied. Using UV-vis spectrophotometry, it was shown that complex 1 decomposes in the solution. The theoretical electronic spectrum in the UV and visible regions was calculated for this complex using a TDDFT method, and an analysis of molecular orbitals of the complex was carried out. It was suggested that the disappearance of the absorption band due to an electronic transition involving the Fe—NO groups is associated with the NO donation. Using quantum chemical calculations, a total energy diagram of the decomposition of complex 1 in DMSO was obtained, and two mechanisms of its transformation, viz., one proceeding through an increase in the coordination number of the iron atom to 6 and the other occurring with breaking the Fe—S bonds with the μ-SCN bridge, were studied.

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来源期刊

Russian Chemical Bulletin 化学-化学综合

CiteScore

2.70

自引率

47.10%

发文量

257

审稿时长

3-8 weeks

期刊介绍： Publishing nearly 500 original articles a year, by leading Scientists from Russia and throughout the world, Russian Chemical Bulletin is a prominent international journal. The coverage of the journal spans practically all areas of fundamental chemical research and is presented in five sections: General and Inorganic Chemistry; Physical Chemistry; Organic Chemistry; Organometallic Chemistry; Chemistry of Natural Compounds and Bioorganic Chemistry.