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首页> 外文期刊>Journal of the Indian Chemical Society >Synthesis, characterization and coordinating properties of an NNS donor system, 5-methyl-3-formylpyrazole-3-pyrrolidinylthiosemicarbazon (HMPzPyr), and it's cobalt(III), nickel(II) and copper(II) complexes
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Synthesis, characterization and coordinating properties of an NNS donor system, 5-methyl-3-formylpyrazole-3-pyrrolidinylthiosemicarbazon (HMPzPyr), and it's cobalt(III), nickel(II) and copper(II) complexes

机译:NNS供体系统,5-甲基-3-甲酰基吡唑-3-吡咯烷基硫代半氨基甲酸酯(HMPzPyr)及其钴(III),镍(II)和铜(II)配合物的合成,表征和配位性能

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摘要

The ligational behaviour of 5-methyl-3-formylpyrazole-3-pyrrolidinylthiosemicarbazone has been demonstrated by isolation and characterisation of its complexes with cobalt(III), nickel(II) and copper(II) with different counterions. Magnetic and spectral features indicate [Co(MPzPyr)2]X (X = Cl, Br, NO3, ClO4 or BF4) as the diamagnetic octahedral species with the ligand in the deprotonated thiol form, while [Ni(HMPzPyr)2]X2 (X = Cl, Br or NO3) is proposed as octahedral complex with the ligand in the neutral thione form. However, at pH ~6, nickel(II) salts afford octahedral bis-nickel(II) complex, Ni(MPzPyr)2, while copper(II) salts in acetonitrile medium give Cu(MPzPyr)X (X - Cl, Br or NO3) with the deprotonated ligand. IR spectra indicate that the pyrazolyl ring nitrogen (~2N), the azomethine nitrogen and the sulphur atom are the points of attachment with the metal ion in all these complex species. The cyclovoltammetric study of copper(II) complexes reveals the quasi-reversible one-electron process (Cu~(II) → Cu~I), where the EPR data confirm the presence of d_(x~2-y~2) ground state of these complexes.
机译:通过分离和表征其与具有不同抗衡离子的钴(III),镍(II)和铜(II)的配合物,已证明了5-甲基-3-甲酰基吡唑-3-吡咯烷基硫基半脲的连接行为。磁性和光谱特征表明[Co(MPzPyr)2] X(X = Cl,Br,NO3,ClO4或BF4)为抗磁八面体,配体为去质子化硫醇形式,而[Ni(HMPzPyr)2] X2( X = Cl,Br或NO3)被提议为具有中性硫酮形式配体的八面体络合物。但是,在pH〜6时,镍(II)盐会生成八面体双镍(II)配合物Ni(MPzPyr)2,而乙腈介质中的铜(II)盐会生成Cu(MPzPyr)X(X-Cl,Br或NO3)与去质子化的配体。红外光谱表明,在所有这些复杂物种中,吡唑基环氮(〜2N),偶氮甲碱氮和硫原子是与金属离子的连接点。铜(II)配合物的伏安法研究揭示了准可逆单电子过程(Cu〜(II)→Cu〜I),其中EPR数据证实了d_(x〜2-y〜2)基态的存在这些复合体。

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