簇合物(μ-SC_6H_5)(μ-P(SC_6H_5)_2)Fe_2(CO)_6的合成和晶体结构

SYNTHESIS AND CRYSTAL STRUCTURE OF CLUSTER (μ-SC_6H_5)(μ-P(SC_6H_5)_2)Fe_2(CO)_6

用Fe_3(CO)_(12)与亚磷酸三硫代苯酯P(SC_6H_5)_3反应得到标题化合物。P(SC_6H_5)_3以其裂解分子片SC_6H_5和P(SC_6H_5)_2配位。用X-ray衍射技术测定了该化合物的晶体结构,晶体属正交晶系,空间群为Pbca,a=17.422(7),b=10.634(6),c=28.987(12)A;V=5370A^3,z=8,D_c=1.579g·cm^(-3)。由直接法和差值Fourier合成解出全部非氢原子坐标,并用全矩阵最小二乘法修正,最后偏离因子R=0.054,R_w=0.058, 分子结构中心的Fe_2SP折叠环沿S…P线或沿Fe-Fe键折叠的二面角(分别为76.1°和82°)比其它具有中心Fe_2S_2,Fe_2P_2和Fe_2SP折叠环的类似化合物中的相应值小,Fe-Fe键长为2.572A,Fe-S(1)-Fe=68.6°,Fe-P-Fe=70.7°。

The title compound was obtained by the reaction of Fe_3(C?)_(12) with phosphorotri-thious acid triphenyl ester P(SC_6H_5)_3. Ligand precursor P(SC_6H_5)_3 coordinated tothe cluster by its cleaved fragments SC_6H_5 and P(SC_6H_5)_2. The crystal structure ofthe compound has been determined by a single crystal X-ray diffraction method. Thecrystal is orthorhombic, space group belongs Pbca,a=17. 422(7), b=10. 634(6), c=28. 987(12); V=5370A^3, z=8, D_c=1. 579g·cm^(-3). Coordinates of all nonhydrogenatoms were delermined by direct method and difference Fourier synthesis, with 3531observable reflections (I≥3σ(I_0)) refined by a full-matrix least-squares procedureso that the final R=0.054, R_w=0.058. The dihedral angle of the folded Fe_2SPring along the S…P line or the Fe--Fe bond (76. 1°or 82°, respectively,) is muchsmaller than that for other similar compounds with the central Fe_2S_2 or Fe_2P_2 or Fe_2.SP folded rings. Fe--Fe=2. 572(2) A, Fe--S(1)--Fe=68. 6°(1), Fe--P--Fe=70. 7°(1).