Studies of Syntheses and Reactions of Layred Antimony Compounds with Anions between the Layrs

层间阴离子层状锑化合物的合成及反应研究

• 批准号: 07804040
• 负责人: IMOTO Hideo
• 金额: $ 1.47万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07804040/
• 关键词: layred compound; antimony compound; rhenium compound; oxide; metal-metal bonding; 層状酸化物

1. A new layr compound (Sb_4O_5)(ReO_4)_4 has been prepared by thermal decomposition of a hydrate compound SbOReO_2・2H_2O in a sealed silica tube and its structure was determined by single-crystal X-ray diffraction. The structure contains cationic layrs of (Sb_4O_5)^<2+> extending along the 010 plane in which each antimony atom has three coordinating oxygen atoms in a trigonal-pyramid geometry. These SbO_3 pyramids share their edges and apices to form a two-dimensional layr. Tetrahedral perrhenate ions are between these cationic layrs. Antimony atoms have also long bonds (2.5-2.75*) with the oxygen atoms of the perrhenate ions, and these bonds presumably sustain the three-dimensional structure. Trials to substitute the perrhenate ions with other anions were unsuccessful. Comparison of the structures of the compounds with cationic antimony oxide layrs indicates the importance of the interactions between the anions and the cationic layrs for these structures.2. A new compound SbRe_2O_6 with a Re-Re bond has been prepared by a reaction of SbOReO_4・2H_2O with rhenium metal in a sealed silica tube. X-ray structure determination has shown that the structure is made of Re_2O_6 layrs which are slices of the rutile structure along the 101 plane and antimony atoms connecting the layrs. The Re_2O_6 layrs contain pairs of ReO_6 octahedra sharing an edge where the Re-Re distance is 2.519 (1)*. Though in BiRe_2O_4 having similar structure oxygen atoms in the Re_2O_6 layrs is disordered, SbRe_2O_6 has ordered stacking of the layrs in the sequence of ABAB.

1.本文报道了一种新的层状化合物（Sb_4O_5）（ReO_4）_4的合成方法，该化合物是由水合化合物SbOReO_2·2H_2O在密封石英管中热分解而成的。该结构包含沿沿着0 10面延伸的（Sb_4O_5）^<2+>阳离子层，其中每个锑原子具有三个配位氧原子，呈三角锥几何构型。这些SbO_3棱锥共享它们的棱和顶点，形成二维层。四面体过氧化氢离子位于这些阳离子层之间。锑原子还与过氧酸根离子的氧原子形成长键（2.5-2.75*），这些键可能维持三维结构。用其他阴离子取代过氧化氢根离子的试验是不成功的。通过对具有阳离子氧化锑层的化合物结构的比较，说明了阴离子与阳离子层之间的相互作用对这些结构的重要性.在密封石英管中，用SbOReO_4·2H_2O与稀土金属反应，合成了一种新的含Re-Re键的化合物SbRe_2O_6。X射线结构测定表明，该结构由Re_2 O_6层和Sb原子组成，Re_2 O_6层是沿101面沿着的金红石结构的薄片。Re_2O_6层由ReO_6八面体对组成，Re-Re距离为2.519（1）*。在结构相似的BiRe_2O_4中，Re_2O_6层中的氧原子是无序的，而SbRe_2O_6层中的氧原子是按ABAB顺序有序堆积的。