Synthesis and reactivity of (amino)(halo)carbenes

• Applicant: Dr. Philipp Grewelinger
• Subject Area: Inorganic Molecular Chemistry - Synthesis and Characterisation
• Term: since 2026
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 583810758

Initially addressed out of fundamental curiosity, stable carbenes have since found widespread application in chemical, biological, and materials sciences. Despite considerable efforts in recent years to promote the structural diversity, there are still carbenes eluding isolation. Among these, halo-carbenes are of particular interest because (1) the substitution of the halogen atom facilitates the production of a variety of other carbenes and (2) the abstraction of the halide could lead to monocoordinated carbocations. However, isolating a stable derivative has not yet been successful due to various problems. The weak C-X bond and the monovalence of the halogen, which inevitably leads to an acyclic structure, are additional destabilizing factors that contribute to the already high reactivity of carbenes in general. However, the Bertrand group recently demonstrated that the selection of a sterically encumbering substituent enables the isolation of a monosubstituted carbene that is stabilized only by a secondary amine. This remains stable in the solid state for months under inert conditions. Similarly, the isolation of a stable (amino)(halo)carbene could be achieved by selecting a suitable substituent, whereas the Böhme group already demonstrated that a chlorocarbene can transiently be obtained by deprotonation of the Vilsmeier reagent. In the proposed research project, I will therefore investigate the synthesis of a suitable ligand and thus develop a feasible route to an (amino)(halo)carbene and subsequently investigate its reactivity.

• DFG Programme: Fellowship
• International Connection: USA
• Host: Professor Dr. Guy Bertrand