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Antioxidant Properties of Lapachol and Its Derivatives and Their Ability to Chelate Iron (II) Cation: DFT and QTAIM Studies.
Bioinorganic Chemistry and Applications ( IF 3.8 ) Pub Date : 2020-03-31 , DOI: 10.1155/2020/2103239 Djafarou Ngouh Pajoudoro 1 , Daniel Lissouck 2 , Baruch Ateba Amana 1 , Joseph Zobo Mfomo 3 , A E B Abdallah 2 , Alfred Aristide Flavien Toze 1 , Désiré Bikele Mama 1
Bioinorganic Chemistry and Applications ( IF 3.8 ) Pub Date : 2020-03-31 , DOI: 10.1155/2020/2103239 Djafarou Ngouh Pajoudoro 1 , Daniel Lissouck 2 , Baruch Ateba Amana 1 , Joseph Zobo Mfomo 3 , A E B Abdallah 2 , Alfred Aristide Flavien Toze 1 , Désiré Bikele Mama 1
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The elucidation of the complexation of lapachol and its derivatives to Fe2+ cation has been done using the density functional theory (DFT). This complexation has been limited to bidentate and tridentate to Fe2+ cation. Geometry optimizations have been implemented in gas and solution phase (water, acetonitrile, chlorobenzene, benzene, and toluene) for ligands at B3LYP/6-311++G (d,p) level of theory using B3LYP/6-31+G(d,p) optimized data as starting point. But, the geometrical optimizations in solution phase of the 22 complexes analyzed of lapachol and its derivatives to Fe2+ cation were restricted to acetonitrile and benzene. The complexation energy and the metal ion affinity (MIA) have also been calculated using the B3LYP method. The results obtained indicated a proportionality between the MIA values and the retained charge on Fe2+ cation for k2-(O1,O2) modes. But, an inverse proportionality has been yielded between these two parameters for k3-(O2, C=C) tridentate modes. For k3-(O3,C=C) tridentate mode coordination, the higher stability has been obtained. In this latter tridentate coordination in gas phase, the topological analysis of complexes exhibits the fact that the electron density is concentrated between the O3 oxygen atom of the ligand attached to Fe2+ and this metal cation. Moreover, the hydrogen bond strength calculated for isolated ligands (situated between 23.92 and 30.15 kJ/mol) is in the range of normal HBs. Collectively, all the complexation processes have shown to be highly exothermic. Our results have also shown that the electron extraction from Fe2+...Lai complexes is more difficult compared to that from free ligands.
中文翻译:
Lapachol及其衍生物的抗氧化性能及其螯合铁(II)阳离子的能力:DFT和QTAIM研究。
已经使用密度泛函理论(DFT)阐明了拉帕酚及其衍生物与Fe 2+阳离子的络合物。该络合限于二齿和三齿的Fe 2+阳离子。气相和溶液相(水,乙腈,氯苯,苯和甲苯)在B3LYP / 6-311 ++ G(d,p)理论水平使用B3LYP / 6-31 + G( d,p)以优化数据为起点。但是,分析了拉帕索及其衍生物对Fe 2+的22种配合物在溶液相中的几何优化阳离子仅限于乙腈和苯。还使用B3LYP方法计算了络合能和金属离子亲和力(MIA)。获得的结果表明,对于k 2-(O 1,O 2)模式,MIA值与Fe 2+阳离子上的保留电荷成比例。但是,对于k 3-(O 2,C = C)三齿模式,这两个参数之间已产生反比例关系。对于k 3-(O 3,C = C)三齿模式配位,已获得较高的稳定性。在气相中的后三齿配位中,配合物的拓扑分析表明电子密度集中在与Fe 2+连接的配体的O 3氧原子与该金属阳离子之间。此外,针对分离的配体计算的氢键强度(位于23.92和30.15 kJ / mol之间)在正常HBs范围内。总的来说,所有络合过程都显示出很高的放热性。我们的结果还表明,与从自由配体相比,从Fe 2+ ... La i配合物中提取电子更困难。
更新日期:2020-03-31
中文翻译:
Lapachol及其衍生物的抗氧化性能及其螯合铁(II)阳离子的能力:DFT和QTAIM研究。
已经使用密度泛函理论(DFT)阐明了拉帕酚及其衍生物与Fe 2+阳离子的络合物。该络合限于二齿和三齿的Fe 2+阳离子。气相和溶液相(水,乙腈,氯苯,苯和甲苯)在B3LYP / 6-311 ++ G(d,p)理论水平使用B3LYP / 6-31 + G( d,p)以优化数据为起点。但是,分析了拉帕索及其衍生物对Fe 2+的22种配合物在溶液相中的几何优化阳离子仅限于乙腈和苯。还使用B3LYP方法计算了络合能和金属离子亲和力(MIA)。获得的结果表明,对于k 2-(O 1,O 2)模式,MIA值与Fe 2+阳离子上的保留电荷成比例。但是,对于k 3-(O 2,C = C)三齿模式,这两个参数之间已产生反比例关系。对于k 3-(O 3,C = C)三齿模式配位,已获得较高的稳定性。在气相中的后三齿配位中,配合物的拓扑分析表明电子密度集中在与Fe 2+连接的配体的O 3氧原子与该金属阳离子之间。此外,针对分离的配体计算的氢键强度(位于23.92和30.15 kJ / mol之间)在正常HBs范围内。总的来说,所有络合过程都显示出很高的放热性。我们的结果还表明,与从自由配体相比,从Fe 2+ ... La i配合物中提取电子更困难。