New methods for the targeted and selective development of polyphosphorus frameworks

在第一个资助期（36个月）的过程中，我们能够证明我们最初假设的用于多磷化合物的构建，破碎或重排的许多反应途径可以实现。该项目计划总时间为72个月，我们非常乐观地认为，基于第一阶段的结果，我们的进一步调查也将非常成功。在第一期的探索性研究中，我们将继续追求我们的目标：A)金属配合物碎片上多磷阳离子的配位和多磷框架的结构转化；B)将多磷阳离子还原为中性多磷；C)通过过渡金属磷化物和多磷阳离子的缩合合成新的多磷框架，并在必要时根据我们之前的结果对其进行修改。此外，有趣的多磷酸配合物的成功合成为进一步实现开辟了新的可能性，因此在接下来的项目阶段，我们希望增加另一个子项目D)多磷酸配合物的靶向重排和裂解反应。正如在第一个项目阶段所假设的那样，我们收到了许多配合物，这些配合物具有不同的配位模式，可以与我们目前研究的一些多磷阳离子与各种金属羰基配合。从光化学的角度来看，这些复合物是非常有趣的，这使得它们在光化学行为方面特别有吸引力。由于这个原因，我们想要研究我们的配合物的目标转换的激发，特别是可见光。此外，从项目第一阶段的Toolbox Wolf和Toolbox Weigand中可以得到化合物反应行为的一定系统分类，这为有针对性地利用它们的反应性开辟了新的可能性。当多磷阳离子与金属阴离子反应时，我们经常观察到氯（卤素）引起的多磷阳离子分裂成非常有趣的新化合物。此外，研究还表明，在磷阳离子与金属酸盐的某些反应中，有时金属酸盐阴离子被氧化成氧化态为0的金属配合物，会发生抢位反应，我们现在很好地理解了这一点，现在专门用于合成新的，高活性的合成模块。到目前为止发现的大量反应表明，我们将磷阳离子和金属酸盐结合的概念导致了新的合成基石，我们计划将其用于进一步的缩合反应。

In the course of the first funding period (36 month), we were able to show that many of the reaction pathways originally postulated by us for the construction, fragmentation or rearrangement of polyphosphorus compounds can be realized. The project is planned for a total time of 72 months and we are very optimistic that our further investigations will also be very successful based on the results of the first project phase. In continuation of the exploratory investigations of the first period, we will pursue our goals: A) coordination of polyphosphorus cations on metal complex fragments and structural transformation of the polyphosphorus framework, B) reduction of the polyphosphorus cations to neutral polyphosphans and C) synthesis of new polyphosphorus frameworks by condensation of transition metal phosphides and polyphosphorus cations and, if necessary, modifying them based on our previous results. Furthermore, the successful synthesis of interesting polyphosphido complexes opens up new possibilities for further implementations, so that in the following project phase we want to add another subproject D) Targeted rearrangement and fragmentation reactions of polyphosphido complexes. As already postulated in the first project phase, we received a number of coordination complexes with different coordination modes for some of the polyphosphorus cations with various metal carbonyls that we have examined so far. These complexes are extremely interesting from a photochemical point of view, which makes them particularly attractive in terms of photochemical behavior. For this reason, we want to investigate targeted transformations of our complexes by excitation, especially with visible light. In addition, a certain systematics of the reaction behavior of the compounds can be derived from the Toolbox Wolf and the Toolbox Weigand from the first project phase, which opens up new possibilities for targeted use of their reactivity. We often observe a chloride (halogen) -induced fragmentation of the polyphosphorus cations to extremely interesting new compounds when they are reacted with a metal anions. In addition, it was also shown that in some reactions of the phosphorus cations with metallates, sometimes with oxidation of the metallate anion to a metal complex in oxidation state 0, scrambling reactions occur, which we now understand well and now deploy specifically for the synthesis of new, highly reactive synthesis building blocks. A large number of reactions found so far shows that our concept of combining phosphorus cations and metallates leads to new synthetic building blocks, which we are planning to use in further condensation reactions.