Theoretical Investigations on the Aromaticity and anti-Aromaticity of Metallacycles

• Applicant: Dr. Martin Luff
• Subject Area: Theoretical Chemistry: Electronic Structure, Dynamics, Simulation ; Theoretical Chemistry: Molecules, Materials, Surfaces
• Term: since 2025
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 569059173

The aim of the research project is to gain basic theoretical knowledge and a broad understanding of the electronic structure of metallacycles of various compositions using the Amsterdam Density Functional. Starting from the prototypical, organic, six-membered, aromatic benzene (C6H6), a series of hypothetical metallacycles (e.g. C5H5M, C4H4M2, C3H3M3, M6) will be constructed by consecutive exchange of the CH units with selected (isolobal) transition metal complex fragments (e.g.: M = PtCl, TiF, ...). The electronic structure of these hypothetical molecules will be investigated with a particular focus on the electronic interactions of the present d- and p-electrons of the transition metal complex fragments with their neighbouring atoms and their influence on potential aromatic or anti-aromatic bonding components. Consequently, stability criteria for metal aromatics and metal anti-aromatics are to be revealed and new candidates will be modeled that may potentially be synthetically accessible. Furthermore, based on the acquired knowledge, systems of different ring sizes (n = 3, 4 ,5 ,6), which contain exclusively transition metal complex fragments, so-called "all-metal" metallacycles, will be modeled in the project to gain a broader understanding of the stability of such cyclic systems. The planned research project may in these terms provide a fundamental understanding of the electronic structure of metal aromatics and metal anti-aromatics and reveal essential structural pre-requisites for the construction of such metallacycles. Thus, a general theoretical building plan for the concise synthesis of various metal aromatics and metal anti-aromatics shall be created. The results of the project could therefore pave the way for further experimental investigations on potentially interesting material properties or other applications of metallacycles.

• DFG Programme: WBP Fellowship
• International Connection: Netherlands
• Host: Professor Dr. Matthias Bickelhaupt