and EPR measurements. In contrast, the tetradentate [S2N2] ligand led to a binuclear bis(μ-thiolato) [CoII(S2N2)]2 complex, the structure of which was solved by X-ray crystallography. Each CoII centre was found to reside in an N2S3 square-pyramidal environment in the crystal, the two Co atoms being bridged by one of the two thiolates of an [S2N2] ligand. On the basis of the temperature dependence of
两种不同的
配体 [S2N3py] 和 [S2N2],分别由 2,6-双[1-(2-巯基
苯胺基)乙基]
吡啶和 2,3-双(2-巯基
苯胺基)
丁烷制备,已用于研究
钴与
混合胺氮/
硫供体组协调。五齿[S2N3py]
配体产生单核[CoII(S2N3py)]复合物,发现其仅在低温
氩气下稳定,并根据1H NMR表征为具有高自旋CoII状态和EPR 测量。相比之下,四齿 [S2N2]
配体导致双核双(μ-
硫醇基)[CoII(S2N2)]2 复合物,其结构通过 X 射线晶体学解析。发现每个 CoII 中心都位于晶体中的
N2S3 方形锥体环境中,两个 Co 原子由 [S2N2]
配体的两个
硫醇之一桥接。基于磁化率的温度依赖性,发现两个 CoII 中心处于低自旋状态,并且略微反
铁磁耦合,绝对 J 值小于 3 cm-1。在 CH3SO3H 存在下的充气
CH2Cl2 中,双核复合物被证明在其混合价态 [CoII/CoIII]