羰基铁-硫醇-三乙胺反应体系的研究——铁硫磷簇合物(μ-PhClP)(μ-RS)Fe_2(CO)_6的合成及结构

Study on Reaction System of Iron Carbonyls-mercaptans-Et_3 N——Synthesis and Structures of Iron-phosphorus-sulfur Clusters(μ-PhCIP)(μ-RS)Fe_2(CO)_6

蝶状铁硫磷簇合物的合成,结构及性质的研究是原子簇化学中一个十分有趣的课题,然而迄今为止文献中只报道过三个(1～3)这类簇合物,它们可分别按文献[1～3]制得:

Through the reaction of PhPCl_2 with the intermediates Et_3NH[(μ-CO)(μ-RS)-Fe_2(CO)_6]formed from Fe_3(CO)_(12),RSH and Et_3N,four clusters with general formula(μ-PhPCl)(μ-RS)Fe_2(CO)_6(R=Et,Pr^i,Bu^n,Bu^t)have been prepared and characterized byC/H analysis,MS,IR and ~1H NMR spectroscopy.For a cluster complex with R=But thecrystal structure has been determined by an X-ray diffraction method.Crystals of the com-plex are monoclinic,space group P Z_1/n.The cell parameters are as follows:a=12.134(2),b=12.306(2),c=14.391(3)(?),β=97.77(1)°,z=4,D_x,1.60g·cm^(-3).This molecule con-tains a butterfly-shaped cluster skeleton consisting of Fe_2PS atoms,the group of Bu^t is con-nected to sulfur atom yia an e—bond while phenyl group and chlorine atom are connectedto phosphorus atom via an a—bond and e—bond respectively.The length of Fe—Fe bondequals 2,6017(?).