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

研究基本白磷的反应性是一个实际的研究领域，采用可持续的和原子高效的直接途径来合成可用的有机磷和无机磷化合物。相比之下，合成类似的含砷化合物的路线总是分别通过AsCl3和AsH3进行，这些化合物的应用潜力主要是在半导体技术上。为了克服黄砷作为起始原料的研究中的明显不足，本项目重点研究了黄砷与主族元素化合物的反应行为，到目前为止，几乎没有任何实例。这一点至关重要，特别是考虑到砷主族元素化合物具有很高的应用潜力，我们的相应知识必须得到显著提高。首先，这一应用领域从属于获得这种主要族元素产品及其主要特征的一般学术问题，因此必须以探索性的方式加以推进。此外，还有AS4和P4在尽可能相同的条件下的反应行为的类比和差异的问题，以便评估它们的反应性是否不同(基于不同的E-E键能)以及不同的产物可获得的程度。AS4激活的机制阐明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时物种，因为75As-核磁共振谱不能用来阐明反应途径。然而，混合四面体PnAs4-n(n=1-3)的相对活化，其中1-3个砷原子被磷原子取代，提供了替代31P-核磁共振光谱的可能性。然而，对于n=1和n=2的衍生物，必须开发具有可用数量的适当合成路线。

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.