Department of Chemistry, Faculty of Science, Mansoura University, Mansoura, PO Box 70, Mansoura, Egypt.
Spectrochim Acta A Mol Biomol Spectrosc. 2013 Mar;104:26-34. doi: 10.1016/j.saa.2012.11.008. Epub 2012 Nov 16.
The chelating behavior of ligands based on carbohydrazone core modified with pyridine end towards Co(II), Ni(II) and Cu(II) ions have been examined. The ligands derived from the condensation of carbohydrazide with 2-acetylpyridine (H(2)APC) and 4-acetylpyridine (H(2)APEC). The (1)H NMR, IR data and the binding energy calculations of H(2)APC revealed the presence of two stereoisomers syn and anti in the solid state and in the solution. The (1)H NMR, IR data and the binding energy calculations confirmed the presence of H(2)APEC in one keto form only in the solid state and in the solution. The spectroscopic data confirmed that H(2)APC behaves as a monobasic pentadentate in Co(II) and Cu(II) complexes and as mononegative tetradentate in Ni(II) complex. On the other hand, H(2)APEC acts as a mononegative tridentate in Co(II) complex, neutral tridentate in Ni(II) complex and neutral bidentate in Cu(II) complex. The electronic spectra and the magnetic measurements of complexes as well as the ESR of the copper complexes suggested the octahedral geometry. The bond length and bond angles were evaluated by DFT method using material studio program. The thermal behavior and the kinetic parameters of degradation were determined using Coats-Redfern and Horowitz-Metzger methods. The antioxidant (DDPH and ABTS methods), anti-hemolytic and in vitro Ehrlich ascites of the compounds have been screened.
基于吡嗪端修饰的碳酰肼核心配体对 Co(II)、Ni(II)和 Cu(II)离子的螯合行为进行了研究。配体是由碳酰肼与 2-乙酰基吡啶(H(2)APC)和 4-乙酰基吡啶(H(2)APEC)缩合得到的。(1)H NMR、IR 数据和 H(2)APC 的结合能计算表明,在固态和溶液中存在两种立体异构体顺式和反式。(1)H NMR、IR 数据和结合能计算证实了 H(2)APEC 在固态和溶液中仅以一种酮式存在。光谱数据证实,H(2)APC 在 Co(II)和 Cu(II)配合物中表现为单齿五配位体,在 Ni(II)配合物中表现为单负四配位体。另一方面,H(2)APEC 在 Co(II)配合物中作为单负三配位体,在 Ni(II)配合物中作为中性三配位体,在 Cu(II)配合物中作为中性二配位体。配合物的电子光谱和磁性测量以及铜配合物的 ESR 表明其具有八面体几何构型。通过使用 material studio 程序的 DFT 方法评估了键长和键角。通过 Coats-Redfern 和 Horowitz-Metzger 方法确定了热行为和降解的动力学参数。对化合物的抗氧化(DDPH 和 ABTS 方法)、抗溶血和体外艾氏腹水进行了筛选。