Formation of metal-radical species upon reduction of late transition metal complexes with heteroleptic ligands: an experimental and theoretical study,New Journal of Chemistry

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Formation of metal-radical species upon reduction of late transition metal complexes with heteroleptic ligands: an experimental and theoretical study
New Journal of Chemistry ( IF 2.7 ) Pub Date : 2020-07-13 , DOI: 10.1039/d0nj02447c
Michal Malček _{1,

2,

3,

4,

5} , Júlia Kožíšková _{1,

2,

3,

4,

5} , Peter Herich _{1,

2,

3,

4,

5} , Peter Rapta _{1,

2,

3,

4,

5} , Iryna Stepanenko _{6,

7,

8} , Vladimir B. Arion _{6,

7,

8}

Affiliation

A series of three new metal complexes with selenadiazoloquinolones, known as broad spectrum antibiotics in clinical praxis, namely [Co(E4h)₂(phen)]·8H₂O (1), [Ni(E4h)₂(phen)]·8H₂O (2) and [Cu(E4h)(phen)Cl]·5H₂O (3), have been synthesized and fully characterized by analytical methods, ESI mass spectrometry, single crystal X-ray crystallography, cyclic voltammetry (CV), and in situ EPR/UV-vis-NIR spectroelectrochemistry supported by theoretical calculations. For 1 and 2 two-electron transfer leads to the formation of a paramagnetic dianion with the spin density localized on the two weakly interacting selenadiazole moieties. For 3 the first reduction step represents a reduction process on the central atom, while the second reversible reduction step occurs on the selenadiazole moiety. The formation of a radical anion of selenadiazoloquinolone upon cathodic reduction was confirmed both experimentally and by DFT calculations. The optimized geometries were compared with the geometric parameters resulting from single crystal X-ray diffraction data, and the bonding in 1–3 was inspected via analysis of bond critical points (BCP) under the formalism of Bader's quantum theory of atoms in molecules (QTAIM).

中文翻译：

过渡金属与杂配体还原后形成金属自由基物质的实验和理论研究

一系列带有硒二氮杂喹诺酮类的三种新金属配合物，在临床上被称为广谱抗生素，即[Co（E4 h）₂（phen）]·8H ₂ O（1），[Ni（E4 h）₂（phen）] ·已合成8H ₂ O（2）和[Cu（E4 h）（phen）Cl]·5H ₂ O （3）并通过分析方法，ESI质谱，单晶X射线晶体学，循环伏安法对其进行了全面表征（CV）和原位EPR / UV-vis-NIR光谱电化学得到理论计算的支持。对于1和2双电子转移导致顺磁性双阴离子的形成，其自旋密度位于两个弱相互作用的硒代二唑部分上。对于3，第一还原步骤代表对中心原子的还原过程，而第二可逆还原步骤发生在硒代二唑部分上。通过实验和通过DFT计算证实了在阴极还原时硒代二氮杂喹诺酮的自由基阴离子的形成。将优化的几何形状与单晶X射线衍射数据得出的几何参数进行比较，并根据巴德分子原子量子理论（QTAIM）的形式，通过分析键的临界点（BCP）来检查1-3中的键）。

更新日期：2020-08-03

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