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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Acetylacetonate bis(thiosemicarbazone) complexes of copper and nickel: towards new copper radiopharmaceuticals
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Acetylacetonate bis(thiosemicarbazone) complexes of copper and nickel: towards new copper radiopharmaceuticals

机译：铜和镍的乙酰丙酮双（硫代半脲）配合物：用于新型铜放射性药物

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摘要

A series of copper(II) and nickel(II) 1,3-bis(thiosemicarbazonato) complexes have been synthesised by the reaction of the metal acetates with pyrazoline proligands. In each case the complexes have an overall neutral charge with a dianionic ligand. The copper 1,3-bis(4-methyl-3-thiosemicarbazonato) complex has been characterised by X-ray crystallography, which shows the copper is in an essentially square-planar symmetric N2S2 environment. The nickel 1,3-bis(4-methyl-3-thiosemicarbazonato) and nickel 1,3-bis(4-phenyl-3-thiosemicarbazonato) complexes have been characterised by X-ray crystallography and show that in these cases the nickel is in a distorted square-planar environment, but the bonding mode of the ligands is unusual; the nickel binds to one of the aza-methinic nitrogen atoms and one hydrazinic nitrogen, creating one five-membered N-N-C-S-Ni chelate ring and one four-membered N-C-S-Ni chelate ring. Interestingly, the X-ray structure of the ethyl analogue {1,3-bis(4-ethyl-3-thiosemicarbazonato) nickel(II)} shows that in this case the nickel is symmetrically coordinated in the usual manner. The nickel complexes are diamagnetic and the different coordination modes are confirmed in solution by NMR spectroscopy. The complexes are susceptible to oxidation in air and a nickel complex, in which the central methylene carbon has been oxidised, has been characterised by X-ray crystallography and NMR spectroscopy. Electrochemical measurements show that the copper complexes undergo a reversible one-electron reduction at biologically accessible potentials.
机译：通过金属乙酸盐与吡唑啉配体的反应，合成了一系列的铜（II）和镍（II）1,3-双（硫代半碳氮杂）。在每种情况下，配合物都具有带有阴离子配体的整体中性电荷。 X射线晶体学表征了铜1,3-双（4-甲基-3-硫代半碳氮杂）络合物，表明铜处于基本呈方形对称的N2S2环境中。 X射线晶体学表征了镍1,3-双（4-甲基-3-硫代半碳氮杂）和镍1,3-双（4-苯基-3-硫代半碳氮杂）配合物，并表明在这些情况下镍是在扭曲的正方形平面环境中，但配体的键合模式不同寻常;镍与氮杂次甲基氮原子之一和一个肼氮原子结合，形成一个五元N-N-C-S-Ni螯合环和一个四元N-C-S-Ni螯合环。有趣的是，乙基类似物{1,3-双（4-乙基-3-硫代半碳氮杂）镍（II）}的X射线结构表明，在这种情况下，镍以通常的方式对称配位。镍络合物是反磁性的，并且通过NMR光谱法在溶液中确认了不同的配位模式。该配合物在空气中易被氧化，并且其中的中心亚甲基碳已被氧化的镍配合物已经通过X射线晶体学和NMR光谱表征。电化学测量表明，铜络合物在生物可接近的电势下经历可逆的单电子还原。

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