若干含氧桥双核钼(Ⅴ)原子簇化合物的研究

Structural Studies on Some Cluster Compounds of Dimeric Oxomolybdates Containing Oxo Bridges

本文在测定了五个新颖双核钼(Ⅴ)簇合物的晶体结构(QH)_4[Mo_2O_4(NCS)_6](1),H(PyH)_3·[Mo_2O_4(C_2O_4)_2(H_2O)_2]_2·2H_2O(2),(QH)_3[Mo_2O_4(C_4H_3OCOO)(NCS)_4](3),(QH)_3[Mo_2O_4·(CH_3OH)(NCS)_5](4)和(PyH)_4[Mo_2O_3(SO_4)(NCS)_6](5)以及文献报道该类型化合物结构数据的基础上,综述了含氧桥双核钼(Ⅴ)簇合物的结构特征,并应用SCC-EHMO方法探讨了该类型化合物的电子结构和成簇机理,最后用简正坐标分析法,研究了含氧桥双核钼(Ⅴ)化合物簇胳单元[Mo_2O_4]^(2+)和[Mo_2O_3SO_4]^(2+)的振动结构及其红外谱带归属。

On the basis of five crystal and molecular structures of novel dimeric di-μ-oxo, di- μ-oxo-μ-carboxylato and μ-oxo-μ-so_4 bridged oxomolybdates (V) (QH)_4 [Mo_2O_4 (NCS)_6]. H (PyH)_3 [Mo_2O_4 (C_2O_4)_2 (H_2O)_2]_2·2H_2O, (QH)_3 [Mo_2O_4 (C_4H_3OCOO) (NCS)_4], (PyH)_3· [Mo_2O_4(CH_3OH) (NOS)_5] and (PyH)_4[Mo_2O_3SO_4(NCS)_6] determined by authors and the data reported in literatures, the structural characteristic of oxodimolybdates containing oxo bridges are summarized. The electronic structure and forming mechanism for dimeric cluster has been studied by SCC-EHMO method. A normal coordinate analysis on Mo_2O_4^(2+) and Mo_2O_3SO_4^(2+) core have been carried out and the infrared spectra are assigned.