Yellow Arsenic as starting Material– Differences and Similarities in Its Reactivity to White Phosphorus

研究初级白磷的反应性是一个实际的研究领域，采取可持续和原子高效的直接途径合成可用的有机磷和无机磷化合物。相比之下，类似的含砷化合物的合成路线，其应用潜力主要是在半导体技术中，通常分别通过AsCl3和AsH3进行。为了克服利用黄砷作为起始材料的研究中存在的明显缺陷，本项目重点研究黄砷对主要族元素化合物的反应行为，目前还没有任何例子。这是至关重要的，特别是考虑到砷主族元素化合物具有很高的应用潜力，我们的相关知识必须大大增强。首先，这一应用领域从属于此类主要类群元素产品的获取途径及其主要特征等一般性学术问题，因此必须以探索性的方式推进。此外，在尽可能相同的条件下，As4和P4之间的类比和反应行为的差异也存在问题，以便评估它们的反应性是否不同（基于不同的E-E键能），以及不同的产物在多大程度上可以接近。阐明As4活化的机制是该项目的另一个中心目的。为了实现后者，有必要捕获和分离瞬态物质，因为75As-NMR波谱不能用于阐明反应途径。然而，混合四面体PnAs4-n （n =1-3）的比较活化，其中一到三个砷原子被磷原子取代，提出了使用31P-NMR谱代替的可能性。然而，对于n = 1和2的衍生物，必须开发合适的合成路线，并有可用的量。

Investigating the reactivity of elementary white phosphorus is an actual area of research, taking both a sustainable and an atom-efficient direct path towards the synthesis of usable organo-phosphorus and inorganic phosphorus compounds. In contrast, the synthetic route to analogous, arsenic-containing compounds whose application potential is mainly in semiconductor technology always proceeds via AsCl3 and AsH3, respectively. To overcome the obvious deficit in the research of the usage of yellow arsenic as a starting material, our project focuses the investigation of the reaction behavior of yellow arsenic towards compounds of main group elements for which, so far, hardly any examples are known. This is crucial especially with regard to the prospectively high application potential of arsenic main group element compounds, and our corresponding knowledge has to be significantly enhanced. In the first instance, this field of application is subordinate to the general academic question of the access to and the principal characteristics of such main group element products and therefore has to be advanced in an explorative manner. Further, there is the question of the analogy and the differences in the reaction behavior between, on the one hand, As4 and, on the other hand, P4, under as much as possible identical conditions in order to evaluate as to whether their reactivity differs (based on the different E–E bond energies) and as to what extent different products become accessible. The mechanistic elucidation of the As4 activation is another central purpose of this project. To achieve the latter, it is necessary to trap and isolate transient species, as the 75As-NMR spectroscopy cannot be used to elucidate the reaction pathway. However, the comparative activation of the mixed tetrahedra PnAs4-n (n =1-3), in which one to three arsenic atoms were replaced by phosphorus atoms, presents a possibility to use the 31P-NMR spectroscopy instead. However, for the derivatives with n = 1 and 2, suitable synthetic routes with usable quantities have to be developed.