Bis-thiosemicarbazones derived from the β-diketone benzoylacetone (H₃banR, R = Me, Et, Ph) are potentially tetradentate N₂S₂ ligands whose coordination chemistry with copper is reported. In the absence of oxygen and in the presence of base they form anionic Cu^II complexes of the fully deprotonated ligands [Cu^II(banR)]^–. Upon exposure to atmospheric oxygen they undergo a complex series of reactions leading to two types of products; one a ligand oxidised ketone complex [Cu^II(banRO)] and the other an unprecedented dimeric di-Cu^III complex [(Cu^III(banR))₂] depending on the R substituent. Time-resolved UV-vis spectroscopy, cyclic voltammetry, spectroelectrochemistry, and electron paramagnetic resonance (EPR) spectroscopy have been used to identify intermediates on the way to stable products formed under both anaerobic and aerobic conditions. It is found that both ligand-centred and Cu-centred oxidation reactions are occurring in parallel leading to this unusually complicated mixture of products.

衍生自β-二酮苯甲酰丙酮（H ₃ banR，R = Me，Et，Ph）的双硫代半咔唑类化合物可能是四齿的N ₂ S ₂配体，据报道其与铜的配位化学。在不存在氧和碱的情况下，它们形成完全去质子化的配体[Cu ^II（banR）] ^–的阴离子Cu ^II络合物。暴露于大气中的氧气后，它们会经历一系列复杂的反应，从而产生两种类型的产物。一个是配体氧化的酮络合物[Cu ^II（banRO）]，另一个是前所未有的二聚二-Cu ^III络合物[（Cu ^III（banR））₂取决于R取代基。时间分辨紫外可见光谱，循环伏安法，光谱电化学和电子顺磁共振（EPR）光谱已被用于鉴定在厌氧和需氧条件下形成稳定产物途中的中间体。发现以配位体为中心的氧化反应和以铜为中心的氧化反应同时发生，导致这种异常复杂的产物混合物。