Zinc(II) thione and selone complexes: The effect of metal redox activity on ligand-based oxidation
Zinc(II) thione and selone complexes: The effect of metal redox activity on ligand-based oxidation
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DOI：
10.1016/j.ica.2019.119379
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发表时间：
2020-03
影响因子：
2.8
通讯作者：
Bradley S. Stadelman;Jaime M. Murphy;Amanda M. Owen;Rodrigo Castro-Ramírez;Haydan C. Smith;Caleb Cohen;Lynn X. Zhang;C. A. Bayse;C. McMillen;N. Barba-Behrens;Julia L. Brumaghim
中科院分区：
文献类型：
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作者：
Bradley S. Stadelman;Jaime M. Murphy;Amanda M. Owen;Rodrigo Castro-Ramírez;Haydan C. Smith;Caleb Cohen;Lynn X. Zhang;C. A. Bayse;C. McMillen;N. Barba-Behrens;Julia L. Brumaghim
硫酮和硒酮配体优先氧化以保护氧化还原活性金属免受氧化，但硫酮或硒酮配位对氧化还原非活性金属的影响尚未研究。因此，我们合成了Zn（L）2Cl 2和[Zn（L）4]2+（L =N，N′-二甲基咪唑[dmit]和硒酮[dmit]）的配合物，并将它们的电子光谱和密度泛函理论（DFT）计算结果与Fe（II）配合物进行了比较. Zn（dmit/dm 3）2Cl 2配合物也被H2 O2氧化，导致dmit和dm 3配体的氧化和C双键S/Se键断裂。电化学研究表明，氧化还原非活性锌（II）的协调，dmit和dmise为基础的氧化电位相对于那些类似的氧化还原活性的Fe（II）配合物降低，表明金属离子的氧化还原活性显着影响的配体的氧化还原性能。
Thione and selone ligands preferentially oxidize to protect redox active-metals from oxidation, but the effects of thione or selone coordination to a redox-inactive metal have not been examined. Therefore, Zn(II)-containing thione and selone complexes of the formulae Zn(L)2Cl2and [Zn(L)4]2+(L =N,N′-dimethylimidazole thione, dmit, and selone, dmise) have been synthesized and their properties, including electronic spectra and DFT calculations, compared with analogous Fe(II) complexes. The Zn(dmit/dmise)2Cl2complexes were also oxidized with H2O2, resulting in oxidation and Cdouble bondS/Se bond cleavage of the dmit and dmise ligands. Electrochemical studies show that upon redox-inactive Zn(II) coordination, dmit- and dmise-based oxidation potentials decrease relative to those of analogous redox-active Fe(II) complexes, demonstrating that the redox activity of the metal ion significantly effects the redox properties of the ligands.