Reactions of Halides and (Pseudo)Halidometallates of V, Cr, Mn, Fe, Co, and Ni in liquid, anhydrous Ammonia

V、Cr、Mn、Fe、Co 和 Ni 的卤化物和（准）卤代金属盐在液态无水氨中的反应

• 批准号: 524000768
• 负责人: Professor Dr. Florian Kraus
• 金额: --
• 依托单位: Fachgebiet 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/524000768?language=en
• 关键词: Reactions; Halides; Pseudo; Halidometallates; Cr

While the chemistry of the hydroxides and the oxides can be considered intensively researched - some even call it completed - there are still gaps in the "ammonium system" even today. This is particularly noticeable in the case of the transition metals, with regard to homo- and heteroleptic ammine, amido and imido complexes as well as ammoniates of these metal compounds. We use the term "ammoniate" analogously to "hydrate". The term ammoniate is used to describe compounds that contain more weakly bound "crystal ammonia molecules", i.e. that do not act as ligands of a central atom. Higher ammoniates are generally not stable at room temperature, so they have rarely been studied in more detail in the past. Mononuclear ammine complexes of certain elements, such as those of Cr, Co, Pt, etc., are often quite stable and have therefore naturally been studied particularly intensively. They founded and shaped coordination chemistry as "Werner complexes". We do not consider main group metal or organometallic compounds in this project, nor do we want to deal with the 4d and 5d metals here. We likewise exclude at this point the compounds of Sc, Ti, Cu, and Zn. Copper is to be studied in a separate project of "Coin and Platinum Metals in Ammonia", zinc is already dealt with in other ongoing projects, Sc and Ti we want to deal with elsewhere. Similarly, the binary and ternary nitrides of the 3d metals, which are already quite well studied, are not the target of our experiments. For reasons stated below, we also do not consider azides, nitrates, hydroxides, aquocomplexes, or hydrates. We want to investigate how the (pseudo)binary and (pseudo)ternary halides and pseudohalides of the 3d metals V, Cr, Mn, Fe, Co and Ni, respectively their metallate complexes, react with and in anhydrous ammonia (anhydrous NH3, aNH3) in the temperature range from circa -78 °C to +70 °C under autogenous NH3 pressure, in the ammonoacidic, -neutral and -basic range and optionally in the presence of foreign ions, and which products, mononuclear and polynuclear homo- and heteroleptic amine, amido, imido and (pseudo)halide complexes and their ammoniaates, are formed.

虽然氢氧化物和氧化物的化学性质可以被认为是深入研究的-有些人甚至称之为完成-但即使在今天，“铵系统”仍然存在空白。这在过渡金属的情况下，就同配位和杂配位的氨合物、酰氨基和酰亚胺络合物以及这些金属化合物的氨化物而言是特别明显的。我们使用术语“氨化”类似于“水合”。术语氨化物用于描述含有更弱结合的“晶体氨分子”的化合物，即不充当中心原子的配体的化合物。高级氨化物在室温下通常不稳定，因此过去很少对其进行更详细的研究。某些元素如Cr、Co、Pt等的单氨络合物，通常相当稳定，因此自然被特别深入地研究。他们创立并塑造了配位化学“维尔纳配合物”。我们在这个项目中不考虑主族金属或有机金属化合物，也不想在这里处理4d和5d金属。在这一点上，我们同样排除了Sc、Ti、Cu和Zn的化合物。铜将在一个单独的项目“氨中的硬币和铂金属”中进行研究，锌已经在其他正在进行的项目中处理，钪和钛我们想在其他地方处理。同样地，三维金属的二元和三元氮化物，已经被很好地研究过了，也不是我们实验的目标。由于以下原因，我们也不考虑叠氮化物、硝酸盐、氢氧化物、水络合物或水合物。我们想研究3d金属V、Cr、Mn、Fe、Co和Ni的（准）二元和（准）三元卤化物和准卤化物，分别是它们的金属配合物，如何与和在无水氨中反应（无水NH3，aNH 3），在自生NH3压力下，在约-78 °C至+70 °C的温度范围内，在氨酸中，- 中性和-碱性范围，并任选地在外来离子存在下，并且形成单核和多核同配和杂配胺、酰氨基、亚氨基和（假）卤化物络合物及其氨化物。