Max M. Hansmann

Mesoionic N ‐heterocyclic olefins (mNHOs) have recently emerged as a novel class of highly nucleophilic and super‐basic σ‐donor compounds. Making use of these properties in synthetic polymer chemistry, it is shown that a combination of a specific mNHO and a Mg‐based Lewis acid (magnesium bis(hexamethyldisilazide), Mg(HMDS) 2 ) delivers poly(propylene oxide) in quantitative yields from the polymerization of the corresponding epoxide (0.1 mol% mNHO loading). The initiation mechanism involves monomer activation by the Lewis acid and direct ring‐opening of the monomer by nucleophilic attack of the mNHO, forming a zwitterionic propagating species. Modulation of the mNHO properties is thereby a direct tool to impact initiation efficiency, revealing a sterically unencumbered triazole‐derivative as particularly useful. The joint application of mNHOs together with borane‐type Lewis acids is also outlined, resulting in high conversions and fast polymerization kinetics. Importantly, while molar mass distributions remain relatively broad, indicating faster propagation than initiation, the overall molar masses are significantly lower than found in the case of regular NHOs, underlining the increased nucleophilicity and ensuing improved initiation efficiency of mNHOs.