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 P-31 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.

Automated summary

This study developed a transition metal-free catalyst for the preparation of high molar weight polyphosphinoboranes, overcoming the interference of transition metal impurities on the reproducibility of material properties.