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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >The utilization of solid state chemistry reaction routes as new syntheses strategies for the coordination chemistry of rare earth amides
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The utilization of solid state chemistry reaction routes as new syntheses strategies for the coordination chemistry of rare earth amides

机译：固态化学反应路线的利用作为稀土酰胺配位化学的新合成策略

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Solvent free high-temperature reactions in melts are well known procedures in Solid-State Chemistry. Although the reaction conditions are extreme considering the properties of organic ligands they can also be utilized for Coordination Chemistry and offer a fruitful alternative to usual solvent treatments. This includes the chemistry of organic amides of the rare earth elements. The avoidance of any solvent renders novel homoleptic complexes accessible but also implies difficulties bound to the solid state of the reaction mixtures. The high chemical affinity of the rare earth elements towards halides and especially oxygen limits known homoleptic amides obtained via solvent treatments mostly to multi-chelating ligands like porphyrines, calix-pyrroles etc. With no special conditions met like a high steric demand, solvent molecules as cocoordinating partners enforce the formation of heteroleptic species. This influence can be avoided by the use of completely solvent free reactions, such as melt reactions in which a solid is reacted directly with a melt or with a substance under solvothermal conditions. The high reactivity of the rare earth metals allows the direct oxidation with amines and thus to use high-temperature reactions for the formation of rare earth amides. This includes homoleptic compounds from simple ligands. Crystallization under reaction conditions is possible; no re-crystallization step is necessary preventing the risk of a change of the chemical character of the products. Additionally, the solubility of rare earth elements in liquid ammonia under formation of an electride solution enlarges the temperature range of these oxidation reactions down to the melting point of ammonia. It further enhances the reactivity of the metals and less N-H acidic and thermally less stable amines can be introduced into these syntheses enabling the formation of meta stable products. The crystal structures and hence the properties of the products of both high- and low-temperature oxidation of rare earth metals with amines strongly differ from reactions carried out in classic solvents. Thus reaction routes frequently used in Solid State Chemistry can well be utilized for Coordination Chemistry and offer alternatives to classic solvent based synthesis, particularly if certain properties like homoleptic character or the coordination of elements with a low chemical affinity are aimed for.
机译：熔体中无溶剂的高温反应是固态化学中众所周知的程序。尽管考虑到有机配体的性质，反应条件非常苛刻，但它们也可用于配位化学，并为常规溶剂处理提供了丰硕的替代方法。这包括稀土元素的有机酰胺化学。避免使用任何溶剂使新型均相络合物易于使用，但也意味着难以与反应混合物的固态结合。稀土元素对卤化物的高化学亲和力，尤其是氧，限制了通过溶剂处理获得的已知均酰胺，主要是对多螯合配体（如卟啉，杯盖吡咯等）的反应。在没有特殊条件的情况下，如高空间需求，溶剂分子协调伙伴强制形成杂合物种。可以通过使用完全无溶剂的反应来避免这种影响，例如在溶剂热条件下将固体直接与熔体或物质反应的熔融反应。稀土金属的高反应活性允许其与胺直接氧化，因此可以使用高温反应来形成稀土酰胺。这包括来自简单配体的均配化合物。在反应条件下结晶是可能的。无需进行重结晶步骤即可防止产品化学特性发生变化的风险。另外，稀土元素在形成电子溶液时在液态氨中的溶解度将这些氧化反应的温度范围扩大到氨的熔点。它进一步增强了金属的反应性，并且可以将较少的N-H酸性和热稳定性较差的胺引入这些合成物中，从而形成亚稳定的产物。稀土金属与胺的高温和低温氧化产物的晶体结构以及由此产生的性能与传统溶剂中进行的反应有很大不同。因此，固态化学中经常使用的反应路线可以很好地用于配位化学，并为传统的基于溶剂的合成方法提供了替代方法，特别是在要寻求某些特性（例如均聚物特性或化学亲和力低的元素配位）的情况下。

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