Syntheses, Structures, and Characterization of Sulfur-Bridged Mixed-Metal Cluster Complexes

混合金属簇合物已被广泛研究。最重要的是，许多人的兴趣都集中在(不完整的)立方体型星系团上。本文报道了不完全立方烷型水族离子[Mo_3S_4(H_2O)_9]~(4+)与金属(Fe、Co、Ni、铜、锡、锂)或金属离子(Sn^&lt；2+&gt；)的反应，得到了具有Mo_3MS_4核的混合金属立方烷型水族离子。到目前为止，已经报道了三种立方类型的混合金属芯：单芯、双芯和夹心。发现了一种新的取代反应：Mo_3MS_4^&lt；4+&gt；(AP)+Cu_&lt；2+&gt；--gt；Mo_3CuS_4^&gt；(Aq)+M^&lt；2+&gt；(M=Fe，Ni)2.对不完全立方烷型硫代或氧桥型钼簇合物[Mo_3S_4(H_2O)_9]^&lt；和[Mo_3O_4(H_2O)_9]和[Mo_3O_4(H_2O)_9]^&lt；4+&gt；采用DV-Xα方法，其中采用斯莱特跃迁方法得到了较好的结果。分别以(NH_4)_2MoS_4和(NH_4)_2WS_4为原料合成了[Mo_3S_4(H_2O)_9]和[W_3S_4(H_2O)_9]和[W_3S_4(H_2O)_9]的简便合成方法。新合成了混合金属clusters[(H_2O)_9Mo_3S_4SbS_4Mo_3(H_2O)_9]^&lt；8+&gt；，[Mo_3InS_4(pts)_2-(H_2O)_&lt；10&gt；]^&lt；3+&gt；，和[Mo_2WNiS_4(H_2O)_&lt；10&gt；]^&lt；4+&gt；，并用X-射线单晶衍射法测定了它们的结构。对这些化合物也进行了电化学分析。

Mixed-metal cluster compounds have been studies extensively. Above all, mucti interest has been focused on(incomplete)cubane-type clusters. We have reported the reaction of the incomplete cubane-type aqua ion [Mo_3S_4(H_2O)_9]^<4+> with metals(Fe, Co, Ni, Cu, Sn, and lig)or metal ion(Sn^<2+>) to give mixed metal cubane-type aqua cluster ions with Mo_3MS_4 cores. Three kinds of cubanetype mixed metal cores have been reported so far : single, double, and sandwich.The following are main results obtained.1. A new type of replacement reactions has been found.Mo_3MS_4^<4+> (ap) + Cu_<2+> -> Mo_3CuS_4^<4+> (aq) + M^<2+> (M = Fe, Ni)2. Molecular orbital calculations have been done on incomplete cubane-type sulfide- or oxo-bridged molybdenum cluster compounds [Mo_3S_4(H_2O)_9]^<4+> and [Mo_3O_4(H_2O)_9]^<4+> using DV-Xalpha method, where Slater transition method was applied to get better results.3. Facile synthetic methods for [Mo_3S_4(H_2O)_9]^<4+> and [W_3S_4(H_2O)_9]^<4+> have been developed using (NH_4)_2MoS_4 and (NH_4)_2WS_4, respectively.4. Mixed metal clusters[(H_2O)_9Mo_3S_4SbS_4Mo_3(H_2O)_9]^<8+>, [Mo_3InS_4(pts)_2-(H_2O)_<10>]^<3+>, and [Mo_2WNiS_4(H_2O)_<10>]^<4+> have been newly synthesized and the structures determined by X-ray crystallography. Electrochemical analyses of these compounds have also been done.