某些镍(II)配合物的异常磁矩和零场分裂

R. Ranjan, Navneet Sinha, Sahdeo Kumar, C. Chandra, Shivadhar Sharma
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引用次数: 1

摘要

用2-硫代-3-乙酰基氢酰脲(TAHN)和2-甲酰基吡啶硫代氨基脲(FPTS)制备了Ni(II)的配合物。根据元素分析和摩尔电导率,这些配合物的分子式为NiL 2 x2,其中L = TAHN或FPTS, X = Cl -, Br -, NCS -, clo4 -。配合物和自由配体的红外光谱显示,TAHN配体通过硫和乙酰氧配位,而FPTS配体通过杂环氮和硫配位到Ni(II)金属离子。这些配合物的磁矩为3.20 ~ 3.25 B.M.,大于d8体系中两个未配对电子对应的磁矩(2.828 B.M.)。电子光谱中四个吸收带的出现揭示了配合物八面体对称性中的四方畸变。计算了零场分裂参数D和其他晶体场参数Dq (xy)、Dq (z)、Dt。结果表明,两种平面配体的四方畸变参数(Dt)均按NCS - < Cl - < Br -的顺序增大,零场分裂参数(D)也按相同的顺序增大。
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Abnormal Magnetic Moment and Zero Field Splitting of Some Nickel (II) Complexes
Some complexes of Ni(II) have been prepared with 2-thio-3-acetyl hydantoin (TAHN) and 2-formyl pyridine thiosemicarbazone (FPTS). On the basis of elemental analysis and molar conductivity, the complexes have been formulated as NiL 2 X 2 , where L = TAHN or FPTS and X = Cl – , Br – , NCS – , ClO 4 – . The infrared spectra of complexes and free ligand reveal that the ligand TAHN is co-ordinated through sulphur and acetyl oxygen, while FPTS ligand co-ordinates through heterocyclic nitrogen and sulphur to Ni(II) metal ion. The magnetic moment of these complexes are found to be 3.20-3.25 B.M. The values are greater than value (2.828 B.M) corresponding to two unpaired electrons of a d 8 -system. The appearance of four absorption bands in their electronic spectra reveal, the tetragonal distortion in the octahedral symmetry of complexes. The zero field splitting parameter(D) and the other crystal field parameters like Dq (xy) , Dq (z) , Dt have been calculated. The results show that, the tetragonal distortion parameter (Dt) increases in the order of NCS – < Cl – < Br – while the zero field splitting parameter (D) also increases in the same order for both the planer ligands.
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