El-Gammal O A, Mostafa M M
Department of Chemistry, Faculty of Science, Mansoura University, P.O. Box 70, Mansoura 35566, Egypt.
Department of Chemistry, Faculty of Science, Mansoura University, P.O. Box 70, Mansoura 35566, Egypt.
Spectrochim Acta A Mol Biomol Spectrosc. 2014 Jun 5;127:530-42. doi: 10.1016/j.saa.2014.02.001. Epub 2014 Feb 22.
The chelation behavior of N-{[(allylamino) thiomethyl] hydrazinocarbonylmethyl} trimethylammonium chloride (H3ATHC) towards VO(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+) and UO2(2+) ions have been studied. The structures of the complexes were elucidated using elemental analyses, spectral (IR, UV-visible, (1)H NMR and ESR and mass) as well as magnetic and thermal measurements. The ligand acted as ON bidentate, ONS tridentate donor forming mononuclear complexes. A tetrahedral geometry for Co(2+), square-planar for Ni(2+) and Cu(2+), an octahedral for Zn(2+) and a square-pyramidal arrangement for VO(2+) complexes were proposed, respectively. The EPR spectra of Cu(2+) and VO(2+) complexes confirmed the suggested geometries with values of α(2) and β(2) indicating that the in-plane σ-bonding and in-plane π-bonding are appreciably covalent, and were consistent with very strong in-plane σ bonding in the complexes. Also, the bond length, bond angle, HOMO, LUMO, dipole moment and charges on the atoms have been calculated. Also, the thermal behavior and kinetic parameters were determined using Coats-Redfern and Horowitz-Metzger methods. Furthermore, the synthesized compounds were screened for their superoxide-scavenging activity in the PMS/NADH-NBT system as well as their scavenging effect on ABTS (2,2'-azino-bis(3-ethyl benzthiazoline-6-sulfonic acid) and 2,2-diphenyl-1-picrylhydrazyl(DPPH) radicals. Among these compounds, the ligand and Zn(2+) complex, exhibited the potent ABTS (2,2'-azino-bis(3-ethyl benzthiazoline-6-sulfonic acid) radical scavenging activity, comparable to that of vitamin C.
研究了N-{[(烯丙基氨基)硫代甲基]肼羰基甲基}三甲基氯化铵（H3ATHC）对VO(2+)、Co(2+)、Ni(2+)、Cu(2+)、Zn(2+)和UO2(2+)离子的螯合行为。通过元素分析、光谱（红外、紫外可见、(1)H NMR、电子顺磁共振和质谱）以及磁性和热测量来阐明配合物的结构。该配体作为ON双齿、ONS三齿供体形成单核配合物。分别提出了Co(2+)的四面体几何构型、Ni(2+)和Cu(2+)的平面正方形几何构型、Zn(2+)的八面体几何构型以及VO(2+)配合物的正方锥排列。Cu(2+)和VO(2+)配合物的电子顺磁共振光谱证实了所提出的几何构型，其α(2)和β(2)值表明面内σ键和面内π键具有明显的共价性，并且与配合物中非常强的面内σ键一致。此外，还计算了键长、键角、最高占据分子轨道、最低未占分子轨道、偶极矩和原子上的电荷。同时，使用Coats-Redfern和Horowitz-Metzger方法测定了热行为和动力学参数。此外，还在PMS/NADH-NBT系统中筛选了合成化合物的超氧化物清除活性以及它们对ABTS（2,2'-联氮-双-(3-乙基苯并噻唑啉-6-磺酸)）和2,2-二苯基-1-苦基肼基（DPPH）自由基的清除作用。在这些化合物中，配体和Zn(2+)配合物表现出与维生素C相当的高效ABTS（2,2'-联氮-双-(3-乙基苯并噻唑啉-6-磺酸)）自由基清除活性。
