Taming, Training and Combining Subvalent Main-Group Cations of Group 13 and 14

在这一扩展项目中，最终目标是弥合从收集较重的第13族阳离子的美丽“蝴蝶”阶段到一个系统之间的差距，该系统具有特殊的结构和成键性能，一旦添加了定义的和商业上可获得的螯合膦配体，就可以产生功能分子，作为反式弯曲二聚体或单独作为类似卡宾的单体，可以激活键。正电荷稳定了单价阶段，促进了还原消除。因此，该提案描述了与项目相关的两个典型催化循环，如氢化硼化反应：一方面，基于氧化加成和还原消除的机理，以及基于氧化加成后形成的Lewis-酸性三价氧化产物的替代的Lewis酸机理。此外，该项目还将扩展刚刚开放的Al(I)阳离子的化学，开放14族芳香络合物(Si-Pb)的通道，并将研究13族和14族阳离子结合成异双金属簇阳离子的情况。特别是，第14族的芳香族化合物实际上是没有先例的，成功的访问将需要丰富的后续化学，例如通过与更多的富含电子的给体反应和玩弄连接的配位的非键NS2轨道的轨道能量。因此，在该项目的第二部分，又一次在新的领域专门寻找“蝴蝶”，这些蝴蝶随后被驯服并发挥作用。因此，该项目的标题表明了我们的目标：驯化、训练和结合13和14基团的亚价主基阳离子

In this extension project, the final goal is to bridge the gap from the stage of collecting beautiful "butterflies" of the heavier Group 13 cations, i.e., compounds with unusual structural and bonding properties, to a system that, upon addition of defined and commercially available chelating phosphane ligands, generates functional molecules that, cooperatively as trans-bent dimers or alone as carbene-analogous monomers, can activate bonds. The positive charge stabilizes the univalent stage and facilitates reductive elimination. Hence, the proposal describes two typical catalytic cycles for resulting project-relevant processes like hydroboration: On the one hand, a mechanism basing on oxidative addition and reductive elimination, and an alternative, Lewis acidic mechanism based on the Lewis-acidic trivalent oxidation products formed after oxidative addition. Further, the chemistry of the Al(I) cations just opened will be extended in the project, access to aromatic complexes of group 14 dications (Si-Pb) will be opened, and the combination of group 13 and 14 cations into heterobimetallic cluster cations will be investigated. In particular, the group 14 dication aromatic complexes are virtually without precedent and successful access would entail rich follow-up chemistry, e.g., by reaction with more electron-rich donors and playing with the orbital energy of the nonbonding ns2 orbitals of the ligated dications. In the second part of the project, therefore, "butterflies" are again specifically sought for in new territory, which are then to be tamed and brought to function. Hence, the title of the project indicates our goals: „Taming, Training and Combining Subvalent Main-Group Cations of Group 13 and 14“