Treatment of complex [（μ-SCH2）2NCH2Ph]Fe2（CO）6 with PPh3 in the presence of decarbonylating agent Me3NO-2H2O afforded the rifle complex [（μ-SCH2）2NCH2Ph]Fe2（CO）5（PPh3） in 70% yield. The new complex was characterized by elemental analysis, IR, and 1H （31p, 13C） NMR spectroscopic techniques as well as by X-ray crystallography. It crystallizes in triclinic, space group P i with a = 9.3016（19）, b = 12.698（3）, c = 13.904（3） A, V = 1519.8（7） A3, Z = 2, C32H26Fe2NOsPS2, Mr = 711.33, Dc = 1.554 g/cm3, μ（MoKa） = 1.187 mm^-1, F（000） = 728, T= 113（2） K, the final R = 0.0288 and wR = 0.0680 for 3982 observed reflections （I 〉 2σ（I））. The PPh3 ligand resides in an axial position of the square-pyramidal geometry of the neighboring Fe atom and trans to the benzene ring in order to minimize the steric repulsion between PPh3 and the benzene ring.
Reaction of [（μ-SCH2）2NPh]Fe2（CO）6 with Ph2PCH2PPh2 in the presence of Me3NO·2H2O gave the title complex [（μ-SCH2）2NPh]Fe2（CO）5（Ph2PCH2PPh2）（1）in 78% yield.The new complex 1 was characterized by elemental analysis,spectroscopy and X-ray crys-tallography.It crystallizes in triclinic,space group P1 with a = 10.832（2）,b = 12.003（2）,c = 15.579（3）,V = 1785.6（6）3,Z = 2,C32H26Fe2NO5PS2,Mr = 819.40,Dc = 1.524 g/cm3,μ（MoKα）= 1.064 mm-1,F（000）= 840,T = 113（2）K,the final R = 0.0543 and wR = 0.1218 for 6203 observed reflections（I 2σ（I））.The Ph2PCH2PPh2 ligand resides in an axial position of the square-pyramidal coordination sphere of the Fe atom and trans to the benzene ring in order to reduce the steric repulsion between Ph2PCH2PPh2 and the benzene ring.
