Xufang Liu

Project title: Probing the Unique Chemistry of Pincer Al(I) Complexes: Synthesis, Reactivities and Theoretical Studies

Host Institution: Technical University of Munich (TUM)

Host Supervisor: Prof. Dr. Shigeyoshi Inoue

Co-host Institution: Technion – Israel Institute of Technology

Co-host Supervisor: Prof. Yitzhak Apeloig

Summary project: Low-valent aluminum chemistry continues to represent a highly attractive research frontier in organometallic chemistry, but isolation of low-valent Al(I) compounds is rather challenging due to their thermodynamic inability. Thus far, monomeric compounds of Al(I) remain especially rare, which commonly feature an amino, alkyl or carbene moiety, and their catalytic applications have never to our knowledge been developed. Considering this early stage in the development of low-valent aluminum chemistry, it would be desirable to extent the chemistry with diverse ligand scaffolds in an attempt to garner more structural and reactivity properties.
Given the easily-tunable steric and electronic properties of pincer-type ligand frameworks, they are proposed to be ideal ligand skeletons for the development of low valent Al compounds. By combining the concepts of “steric protection” and “second sphere coordination” to provide both thermodynamic and kinetic stabilization, a series of novel PEP-ligated Al(I) complexes are expected to be synthesized. We would then explore their unique reactivities towards catalytically relevant small molecules, and develop new catalytic reactions such as defluoroborylation of fluoroarenes and (asymmetric) hydrogenation of olefins/imines, and gain mechanistic insights into the proposed transformations by a combined experimental and theoretical studies. We believe that this project will stimulate new interest in the research of main group element chemistry and also bring great contributions to synthetic chemistry.