过渡金属硫簇的几种簇骼转化反应

Some Types of Skeletal Conversions in Transition Metal Sulfur Clusters

报道了过渡金属硫簇化合物的几种簇骼转化反应，即三核链状簇的转化；双核配合物的组合；Ｍｏ２Ｆｅ７Ｓ８和Ｍｏ２Ｆｅ６Ｓ８两种双立方烷的关联；Ｆｅ４Ｓ４立方烷簇向篮状簇的转化；簇降解以及簇骼原子置换反应等。探讨了配体及氧化还原条件对簇骼转化反应的影响。

Some types of skeletal conversions in transition metal sulfur clusters are reported in this paper.A trinuclear linear cluster Fe(DMF)6[(FeCl2)2MoS4] underwent three modes of skeletal conversions in the presence of various ligands,bidentate R2dtc- leading to a single MoFe3S4 cubane-like cluster, monodentate PhS-leading to double cubane cluster,and the mixed ligands(R2dtc- and PhS-) leading to a tetranuclear linear Mo- Fe- Fe- Mo cluster and a Fe4S4cubane-like cluster.Other skeletal conversions in the metal-sulfur clusters include reductive combinations of dinuclear complexes,degradations of tri- and tetrnuclear clusters,the conversion of Fe4S4 cubane-like cluster into a Fe6S4(μ-SPh) backet cluster,the relative conversion between both double cubanes Mo2Fe7S8 and Mo2Fe6S8,and displacement of skeletal atoms in [Mo3S4(H2O)9]4+.The influences of ligands,redox conditions and steric effect on the skeletal conversions are also discussed.