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，我们最初为多磷化合物的构建、断裂或重排假设的许多反应途径都可以实现。该项目计划总时间为72个月，我们非常乐观地认为，根据第一阶段项目的结果，我们的进一步调查也将非常成功。在第一阶段探索性调查的继续中，我们将追求我们的目标：A）多磷阳离子在金属络合物碎片上的配位和多磷骨架的结构转化，B）多磷阳离子还原成中性多磷，和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骨架，如果需要，根据我们以前的结果进行修改。此外，有趣的多聚膦复合物的成功合成为进一步的实施开辟了新的可能性，因此在接下来的项目阶段，我们希望增加另一个子项目D）多聚膦复合物的靶向重排和断裂反应。正如在第一个项目阶段已经假设的那样，我们收到了一些配位络合物，这些络合物对于我们迄今为止已经研究过的一些聚磷阳离子与各种金属羰基化合物具有不同的配位模式。从光化学的角度来看，这些配合物非常有趣，这使得它们在光化学行为方面特别有吸引力。出于这个原因，我们希望通过激发，特别是可见光，研究我们的复合物的靶向转化。此外，化合物的反应行为的某些系统学可以从第一项目阶段的Wavelet Wolf和Wavelet Weigand中得到，这为有针对性地使用其反应性开辟了新的可能性。我们经常观察到氯化物（卤素）诱导的碎片的聚磷阳离子非常有趣的新化合物，当它们与金属阴离子反应。此外，还表明，在磷阳离子与金属化物的一些反应中，有时金属化物阴离子氧化成氧化态为0的金属络合物，会发生混乱反应，我们现在很好地理解了这一点，现在专门用于合成新的高反应性合成结构单元。到目前为止发现的大量反应表明，我们将磷阳离子和金属化物结合的概念导致了新的合成结构单元，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.