Syntheses and Properties of Higher Dimensional Metal Cluster Complexes

本研究的目的是用溶液法制备导电金属簇合物。在水溶液中，(NH_4)_2Mo_3S(S_2)_61与Na2SO_3反应生成黑色产物。在300ﾟC下加热，产物形成半导体材料。类似的反应在硫酸铜存在的情况下形成了半导体。1与三烷基膦在四氢呋喃中反应生成[Mo_3S_5(Pme_3)_6]_2，[Mo_4S_6(SH)_2(Pme_3)_6]3，[Mo_6S_1；12&gt；(Pet_3)_6]4.2是一个等边三角形簇合物，是在超导Chevrel相中发现的一系列团簇单元中的第一个成员：Mo&lt；3n&gt；S&lt；3n+2&gt；DVXa的计算已经说明了三角形没有变形的原因。3具有规则菱形形状的木筏结构。外周Mo-Mo距离相等，DVXα计算结果与10.4团簇价电子数一致，也有两个熔融三角形的RAFT。这是两个三核簇合物单元水平缩合形成的硫化钼的第一个例子。

The purpose of the present research is the preparation of conducting metal cluster compounds by solution methods. The basic reactions are condensation of smaller cluster complexes by removal of a part of sulfur atoms from the S_2 ligands in the cluster units.When (NH_4)_2Mo_3S(S_2)_6 1 Was reacted with Na_2SO_3 in aqueous solutions, a black product was obtained. Heating of the product at 300ﾟC formed a semiconducting material. Similar reactions in the presence of copper sulfate formed a semi-conductor. It transformed into digenite Cu_9S_5, at 700ﾟC.The reaction of 1 with trialkylphosphines in THF yielded [Mo_3S_5(PMe_3)_6] 2, [Mo_4S_6(SH)_2(PMe_3)_6] 3, and [Mo_6S_<12>(PEt_3)_6] 4.2 is an equilateral triangular cluster complex which is the first member of the series of cluster units Mo_<3n>S_<3n+2> found in the superconducting Chevrel phases. The DVXa calculations have shown the reason why the triangle is not distorted. 3 has a raft structure with a regular rhomboid shape. The peripheral Mo-Mo distances are equal and the DVXalpha calculations are consistent with the number of cluster valence electrons of 10.4 has also a raft with two fused triangles. This is the first example of molybdenum sulfide formed by the horizontal condensation of two trinuclear cluster units.