Stabilization of gold-halogen heteropolycations with borosulfate anions

用硼硫酸根阴离子稳定金卤杂多阳离子

• 批准号: 528508733
• 负责人: Dr. Jörn Bruns
• 金额: --
• 依托单位: Institut für Anorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/528508733?language=en
• 关键词: Stabilization; gold; halogen; heteropolycations; borosulfate

The aim of the planned research project is to stabilize heteropolycations with borosulfate anions. The heteropolycations should always consist of gold and a halogen, whereby the oxidation state of the gold can vary from +1 to +3. The starting point of the experimental work is the synthesis of [Au3Cl4][B(S2O7)2] and [Au2Cl4][B(S2O7)2](SO3). By working under strongly oxidizing conditions in SO3, it has been possible to prepare the aforementioned compounds. These are stabilized by bis-disulfatoborate anions, which can be regarded as weakly coordinating anions. These anions are preferentially formed under these extreme conditions and will also serve for charge compensation of the cationic substructure for most of the compounds of the planned research project. In analogy to the synthesis of [Au3Cl4][B(S2O7)2] and [Au2Cl4][B(S2O7)2](SO3), further Au-Cl heteropolycations will be prepared from the reaction of boric acid with AuCl, AuCl2 and AuCl3 in SO3. Besides the variation of the stoichiometric composition, the influence of temperature on the product formation during the solvothermal reactions will be studied. Subsequently, gold bromides, iodides and fluorides will be used as starting materials. It is expected that the products of the reactions of AuBr and AuBr3 will form structures similar to those found for the chlorides. Since iodide anions are significantly larger and fluoride is significantly smaller, the products obtained should have different cationic substructures. For compounds containing Au2+, substitution with the isovalent cations Pd2+ or Hg2+ should be attempted. [Au2Cl4][B(S2O7)2](SO3) exhibits a wave-like arrangement of square planar coordinated Au2+ as well as Au3+ cations and has been characterized as a one-dimensional metal. Accordingly, after a routine characterization via single crystal and powder X-ray diffraction, IR and Raman spectroscopy as well as thermogravimetry, all obtained products of the research project will be subjected to further studies regarding magnetochemistry and conductivity, depending on the structure and nature of the products. Band structure calculations support the experimental results. For magentochemical measurements, conductivity measurements, XPS and band structure calculations, cooperation agreements have been made with colleagues at the University of Cologne.

计划中的研究项目的目的是用硼硫酸盐阴离子稳定杂多阳离子。杂多阳离子应该总是由金和卤素组成，其中金的氧化态可以从+1到+3变化。实验工作的出发点是[Au_3Cl_4][B（S_2 O_7）_2]和[Au_2Cl_4][B（S_2 O_7）_2]（SO_3）的合成。通过在SO 3中的强氧化性条件下操作，可以制备上述化合物。这些被双二硫酸根硼酸根阴离子稳定，其可被视为弱配位阴离子。这些阴离子优先在这些极端条件下形成，并且还将用于计划研究项目的大多数化合物的阳离子子结构的电荷补偿。 类似于[Au 3Cl 4][B（S2 O 7）2]和[Au 2Cl 4][B（S2 O 7）2]（SO 3）的合成，将通过硼酸与AuCl、AuCl 2和AuCl 3在SO 3中的反应制备另外的Au-Cl杂多阳离子。除了化学计量组成的变化，溶剂热反应过程中的产物形成的温度的影响将进行研究。随后，溴化金、碘化金和氟化物将用作起始材料。预期AuBr和AuBr 3的反应产物将形成与氯化物中发现的结构类似的结构。由于碘阴离子明显较大而氟阴离子明显较小，因此所得产物应具有不同的阳离子亚结构。对于含Au 2+的化合物，应尝试用等价阳离子Pd 2+或Hg 2+取代。[Au 2Cl 4][B（S2 O 7）2]（SO 3）是一种一维金属，Au 2+和Au 3+离子呈波浪形平面配位。因此，在通过单晶和粉末X射线衍射、IR和拉曼光谱以及热重分析进行常规表征之后，将根据产品的结构和性质对研究项目的所有所得产品进行关于磁化学和导电性的进一步研究。 能带结构计算支持实验结果。对于磁化学测量、电导率测量、XPS和能带结构计算，与科隆大学的同事达成了合作协议。