Synthesis and Characterization of Rhenium−Copper Sulfide Cluster Complexes [(Ph₃P)₂N][Re₃(CuX)(μ₃-S)₄Cl₆(PMe₂Ph)₃] (X = Cl, Br, I)

The reaction of a trinuclear rhenium sulfide cluster compound Re3S7Cl7 with dimethylphenylphosphine and CuX2 (X = Cl or Br) or CuX (X = Cl, Br, or I) formed tetranuclear cluster complexes [(Ph3P)2N][Re3(CuX)(μ3-S)4Cl6(PMe2Ph)3] (X = Cl, Br, or I). Their solutions have the characteristic intense blue color with visible spectral bands near 600 nm. Single-crystal X-ray structures show that three μ-S atoms in the intermediate trinuclear rhenium complex coordinate to a copper atom, forming elongated tetrahedral structures in which Re−Cu bonding interaction is negligible (Re−Cu distances are 3.50∼3.54 Å as compared with Re−Re distances ranging from 2.69 to 2.81 Å).三核硫化铼簇合物Re₃S₇Cl₇分别与二甲基苯基膦和二卤化铜（X=Cl或Br）或卤化亚铜（X=Cl、Br或I）发生反应，生成四核簇合物[(Ph₃P)₂N][Re₃(CuX)(μ₃-S)₄Cl₆(PMe₂Ph)₃]（X=Cl、Br或I）。该类簇合物的溶液呈现特征性浓蓝色，在600 nm附近存在明显的可见光谱带。单晶X射线衍射结构分析表明，中间体三核铼配合物中的三个μ-桥连硫原子可与一个铜原子配位，形成拉长的四面体结构；其中铼-铜之间的成键相互作用可忽略不计（铼-铜键长介于3.50~3.54 Å，而铼-铼键长范围为2.69~2.81 Å）。