Low temperature liquid-phase synthesis and properties of solid state metal sulfides which are unstable at high temperatures

六核簇合物[Cr_6S_8(PET_3)_6]与S_8在甲苯中于回流温度下反应，每个簇合物中抽提一个三乙基膦，形成一个十二核簇合物[Cr_&lt；12&gt；S_&lt；16&gt；(PET_3)_&lt；10&gt；]。与Chevrel相化合物类似，二聚体簇合物中的簇团单元之间有一个u_4-S-&gt；铬键和一个弱的铬-铬键。通过对簇合物的循环伏安和磁性测量，证明了簇合物的混合价态的扩展。发现了另一种新的三核钼簇合物[Mo6E8Cl6-(PET3)6l(E=S，Se)]的二聚化反应。所制备的RAFT-型簇合物和四核簇合物中的簇价电子数与稠合芳香族化合物中的pi电子数很好地对应。这种“等电子类比”的含义正在研究中。

Treatment of a hexanuclear cluster complex [Cr_6S_8 (PEt_3) _6] with S_8 in toluene at refluxing temperatures has formed a dodecanuclear cluster complex [Cr_<12>S_<16> (PEt_3) _<10>] by abstraction of one triethylphosphine from each cluster. The dimeric cluster has a mu_4-S---->Cr and a weak Cr-Cr bonds between the cluster units, which are similar to those in the Chevrel phase compunds. The expansion of the mixed valency state of the cluster has been demonstrated in the cyclic voltammetry and magnetic measurements on the cluster complexes. Thus the dimerization can be regarded as the first step to prepare "chromium Chevrel compunds" by low temperature polymerization of molecular clusters.Another novel dimerization of trinuclear molybdenum cluster complexes to form [Mo_6E_8Cl_6- (PEt_3) _6l (E=S,Se) has been found. The number of the cluster valence electrons in the raft-type clusters and the tetranuclear cluster complexes prepared in this study corresponds well to the number of pi-electrons in fused aromatic compounds. The meaning of this "Isoelectronic Analogy" is being studied.