El-Asmy A A, Al-Hazmi G A A
Chemistry Department, Faculty of Science, Mansoura University, Mansoura, Egypt.
Spectrochim Acta A Mol Biomol Spectrosc. 2009 Jan;71(5):1885-90. doi: 10.1016/j.saa.2008.07.005. Epub 2008 Jul 15.
The ligational behavior of 2-hydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone N-substituted thiosemicarbazones towards Ni(II) and Cu(II) ions has been investigated. The isolated complexes were identified by elemental analyses, molar conductance, magnetic moment, IR, UV-vis and ESR spectral studies. The IR spectra indicated that the investigated thiosemicarbazones lost the N(2) proton or the N(2) and OH protons and act as mononegative or binegative tridentate ligands. The ligands containing methoxy group facilitate the deprotonation of OH by resonance more than the SH. Most of the Ni(II) complexes measured subnormal magnetic moments due to square-planar+tetrahedral configuration and supported by the electronic spectra. The percentage of square-planar to tetrahedral was calculated and found in agreement with the ligand splitting energy (10Dq). Also, Cu(II) complexes measured subnormal values due to the interaction between copper centers; the lower the value the higher the interaction. It was found that the substitutent has a noticeable effect on the distortion of the complex. The ESR spectra of some solid Cu(II) complexes at room temperature exhibit g(parallel)>g( perpendicular)>2.0023 confirming a square-planar structure.
研究了2-羟基二苯甲酮和2-羟基-4-甲氧基二苯甲酮N-取代硫代卡巴腙对Ni(II)和Cu(II)离子的配位行为。通过元素分析、摩尔电导率、磁矩、红外光谱、紫外可见光谱和电子顺磁共振光谱研究对分离出的配合物进行了鉴定。红外光谱表明，所研究的硫代卡巴腙失去了N(2)质子或N(2)和OH质子，并作为单负或双负三齿配体起作用。含有甲氧基的配体比SH更容易通过共振促进OH的去质子化。由于平面正方形+四面体构型，大多数测量的Ni(II)配合物的磁矩低于正常值，并得到电子光谱的支持。计算了平面正方形与四面体的百分比，发现与配体分裂能(10Dq)一致。此外，由于铜中心之间的相互作用，Cu(II)配合物测量值低于正常值；值越低，相互作用越高。发现取代基对配合物的畸变有显著影响。一些固体Cu(II)配合物在室温下的电子顺磁共振光谱显示g(平行)>g(垂直)>2.0023，证实为平面正方形结构。
