摘要
以合成为目的，研究了Ｍｏ_３Ｓ_４（ｄｔｐ）_４（Ｈ_２Ｏ）（Ⅰ）、Ｍｏ_３ＯＳ_３（ｄｔｐ）_４（Ｈ_２Ｏ）（Ⅱ）、Ｗ_２Ｓ_４（ｄｔｐ）_２（Ⅲ）等为主的簇合物的反应及其产物。包括配基置换反应，加硫和脱硫反应，簇合反应，簇解和局部氧化反应。讨论了反应物的结构和试剂两个方面对反应的影响，由此总结了若干反应规律。本文还以Ｍｏ_４Ｓ_４（ＯＡｃ）_２（ｄｔｐ）_４和Ｍｏ_３ＸＳ_６（ｄｔｐ）_３Ｙ（Ｘ＝Ｓ，Ｏ；Ｙ＝Ｉ，Ｃｌ）为例，阐述了设计合成的基本思路。
With the purpose of synthesizing Mo(W) clusters, a systematic study on the reactions and their products by using Mo_3S_4 (dtp)_4 (H_2O)(Ⅰ),Mo_3OS_3 (dtp)_4 (H_2O) (Ⅱ) and W_2S_4 (dtp)_2 (Ⅲ) as starting materials is carried out (dtp=S_2P(OC_2H_5)_2). The reactions include the ligand substitution, sulfur addition, desulfurization, cluster construction and collapse as well as local oxidation reaction.The effect of both the structure of starting cluster and the reagents on the reactions is discussed. Some reaction rules have thus been set forth on this basis.Moreover, Mo_4S_4-(OAc)_2 (dtp)_4 and Mo_3XS_6 (dtp)_3Y(X=S,O;Y=I, Cl) have also been selected as two examples to illustrate the basic idea of the design synthesis.
基金
国家自然科学基金
结构化学国家重点实验室资助
