三核钼簇合物配基置换反应——两个三核钼簇合物[Mo_3S_4(DTC)_4(DMF)](EtOH)和[Mo_3S_4(DTC)_4(Py)](Py)_2(H_2O)的合成和晶体结构研究

The Replacement Reaction of Trinuclear Molybdenum Clusters——Synthesis and Crystal Structure of Two Molybdenum Clusters [Mo_3S_4(DTC)_4(DMF)](EtOH) and [Mo_3S_4(DTC)_4(Py)](Py)_2(H_2O)

通过配基置换反应合成出两个新的三核钼簇合物[Mo_3S_4(DTC)_4(DMF)](EtOH(1)和[Mo_3S_4-(DTC)_4(Py)](Py)_2(H_2O)(2)。用X射线衍射法测定了这两个簇合物的晶体结构。簇合物1的空间群为PI,晶胞参数:a=10.624(5),b=11.373(2),c=19.216(5)A;α=87.92(2),β=79.89(3),r=69.44(3);Z=2。簇合物2的空间群为PI,晶胞参数:a=11.505(2),b=11.945(1),c=18.974(2)A;α=99.18(1),β=94.82(1),r=93.84(1)°;Z=2。结构分析结果表明,两个簇合物的簇胳均是{Mo_3S_4}^(4+)的三核钼原子簇。对簇合物中配基对Mo-Mo键的影响以及配基置换反应的规律性进行了讨论。

Two new molybdenum clusters [Mo_3S_4(DTC)_4(DMF)] (EtOH) (1) and [Mo_3S_4(DTC)_4- (Py)] (Py)_2(H_2O) (2) (DTC=Et_2NCS_2^-) have been synthesized by the ligand replacement reaction. The crystal structure of the two clusters have been determined by X-ray diffraction method. Cluster 1 belongs to space group P1 and its cell parameters are: a= 10. 624 (5), b=11.373 (2), c=19.216(5)A; α=87.92 (2), β=79.89 (3),γ= 69.44 (3)°; Z= 4. For cluster 2, space group P1, cell parameters: a=11.505(2), b=11.945(1), c= 18.974 (2)A; α=99.18(1), β=94.82(1), γ=93.84(1)°; Z=2. The results of crystal structure analysis show that both compounds are the trinuclear molybdenum clusters with the {Mo_3S_4^(4+)} cluster skeleton. Also discussed in the article are the influence of Mo- Mo bond by the ligands in this kind of clusters and the regularity of ligand replacement reaction.