簇外环化镍十硼烷簇合物的合成与结构研究

研究了NiCl~2(PPh~3)~2]，B~1~0H~1~0^2^-与硫代苯甲酸的反应，得到四个簇合物，其中三个簇合物(PPh~3)(PhCOS)~2Ni·B~1~0H~1~0]·0.5C~6H~1~4(1)，(PhCOS)~2NiB~1~0H~8(PPh~3)](2)，(PhCOS)~3NiB~1~0H~7(PPh~3)](3)。通过单晶X射线衍射进行了结构研究。三个簇合物均为十一顶巢式构型，并分别存在两个、两个、三个簇外环化的五元环，具有三个环的簇合物至今未见其它文献报道。结构分析表明：簇外环化可以增强Ni－B之间的成键作用。

Synthesis and crystal structures of exo-polyhedral cyclized nickelaundecaborane clusters

Four nickelaundecaborane clusters have been isolated from the reaction of NiCl~2(PPh~3)~2] with B~1~0H~1~0^2^- in the present of PhCOSH. Three of them (PPh~3)(PhCOS)~2Ni· B~1~0H~1~0]·0.5C~6H~1~4 (1), (PhCOS)~2NiB~1~0H~8(PPh~3)](2), (PhCOS)~3NiB~1~0H~7(PPh~3)](3) were characterized by X-ray diffraction analysis. The clusters have nido 11-vertex {NiB~1~0} polyhedral skeletons with two, two and three exo-polyhedral cyclic Ni－S－C－O－B five-membered rings, respectively. The distance between boron atoms participating in exo- polyhedral cyclizations to nickel atom is shorter which shows that cyclization can strengthen the nickel-to-boron bonding.