摘要
利用ＣＳ_２与镉硫化合物在溶剂中反应产生Ｓ^（２－）来合成大核镉硫簇合物，得到了两个新的大核镉硫簇合物，并测定了其晶体结构，化合物（Ⅰ）为（Ｍｅ_４Ｎ）_２［ＳＣｄ_８（ＳＰｈ）_（１２）Ｃｌ_４］，晶体属立方晶系，空间群Ｐａ３，ａ＝２６．７８２（３）Ａ，Ｖ＝１９２１１（４）Ａ~３，Ｄｃ＝１．７５０ｇ／ｃｍ~３，Ｚ＝８。１６３７个衍射点参与修正，Ｒ＝６．９６％，化合物（Ⅱ）为［Ｃｄ（Ｈ_２Ｏ）_６］［ＳＣｄ_８（ＳＰｈ）_（１２）Ｃｌ_４］，晶体属立方晶系，空间群Ｆ４３ｃ，ａ＝２７．５９７（５）Ａ，Ｖ＝２１４９１（７）Ａ~３，Ｄｃ＝１．６０９ｇ／ｃｍ~３，Ｚ＝８。５６５个衍射点参与修正，Ｒ＝４．９９％。两个化合物都含有八核镉簇阴离子，但它们的正离子不同，对称性也不同。本文还讨论了这一合成方法的机理和特点。
The two octanuclear cadmium clusters were prepared through the reaction of cadmium thiolate complexes with CS_2 in organic solvents. The crystals of complex (Ⅰ) , (Me_4N)_2[SCd8-(SPh)_12Cl_4], belong to cubic system,space group Pα3 , α= 26. 782 (3) , V = 19211 (4) ,Dc= 1. 750g/cm3, Z=8. The final R is 0. 0696 for 1637 reflections. The crystal (Ⅱ) , [Cd-(H_2O)_6][SCd_8 (SPh)_12Cl_4], belong to cubic system,space group F43c, α= 27. 597 (5) , V=21491 (7) , Dc= 1. 609g /cm3, Z=8. The final R is 0. 0499 for 565 reflections. The cores of the anions of the two complexes are both octanuclear clusters, but they have different symmetries caused by differenct cations. The synthesis method is also discussed.
基金
国家自然科学基金
关键词
簇合物
合成
晶体结构
镉
硫
octanuclear cadmium-sulfur clusters,synthesis crystal structure
