Calix[4]pyrrolato Aluminate Catalyzes the Dehydrocoupling of Phenylphosphine Borane to High Molar Weight Polymers

High molar weight polyphosphinoboranes represent materials with auspicious properties, but their preparation requires transition metal‐based catalysts. Here, calix[4]pyrrolato aluminate is shown to induce the dehydropolymerization of phosphine boranes to high molar mass polyphosphinoboranes (up to M (n)=43 000 Da). Combined GPC and (31)P DOSY NMR spectroscopic analyses, quantum chemical computations, and stoichiometric reactions disclose a P−H bond activation by the cooperative action of the square‐planar aluminate and the electron‐rich ligand framework. This first transition metal‐free catalyst for P−B dehydrocoupling overcomes the problem of residual d‐block metal impurities in the resulting polymers that might interfere with the reproducibility of the properties for this emerging class of inorganic materials.