钼铁硫原子簇化合物的合成与结构化学——Ⅳ.双类立方烷化合物与酰氯的反应

Synthesis and Structural Studies of Molybdenum-Iron-Sulfur Compounds——IV. Novel Reaction of Pseudo-Dicubane Cluster with Acyl Chloride

我们曾利用类金刚烷结构的多铁巯基化合物(Et_4N)_2[Fe_4(SR)_(10)](R为拉电子的芳基C_6H_5或C_6H_4CH_3)与(Et_4N)_2MoS_4的反应,合成了一系列含有Fe(SR)_6桥的双类立方烷化合物[{Mo(FeL)_3S_4}_2(μ_2-SR)_6Fe]^(z-)(L=SR,z=4;R=Ph,1a;R=o-C_6H_4CH_3,1d;R=m-C_6H_4CH_3,1e;R=p-C_6H_4CH_3,1f)。测定了它们的单晶结构,并开展了磁学研究。确认它们都具有1的阴离子结构,其Mo-Fe-Mo’距离都在7.2A左右。当R为推电子的脂肪族基因(如Et或CH_2C_6H_5)时,其相应的距离为6.6—6.7A。原子距离的数据提示。

Pseudo-dicubane cluster compound (Et_4N)_4[Mo_2Fe_7S_8(SC_6H_5)_(12)] (1a) reacted with acetyl chloride in acetonitrile to give terminally chloride substituted 2a with extrusion of Fe(SC_6H_5)_3 bridge. This novel reaction was characterized by ~1H NMR study and elemental analysis of the product. This is the first time that structure type 1 converting to structure type 2 is observed.