Aluminum and gallium metallacycles as element/carbon-based ambiphiles for small molecule activation

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The aim of this project is to establish novel and so far only sporadically studied intramolecular Al/C- and Ga/C-based ambiphiles. Beyond the systems known from the literature, metallacyclic ambiphiles are developed, which should be able to react as "hidden" Frustrated Lewis Pairs (FLPs), also with small molecules that are difficult to activate, such as NH3, under N-H bond cleavage, ideally reversible. Such reaction behavior is unknown for the FLPs described so far and challenging even for transition metal complexes. Especially in view of the use of N-H-activated ammonia as a readily available and atom-economical nitrogen source in hydroamination, this is of great interest. Building on the results of our preliminary work, the key points of the research project are the targeted fine-tuning, extension and general establishment of metallacyclic Al/C-ambiphiles as well as the consistent extension of the concept of hidden FLPs based on small ring systems by the generation of novel Ga/C-ambiphiles. Systematic studies on bond activation of small molecules and possible catalytic transformations are accompanied by quantum chemical calculations to describe structure, bonding and reactivity.