Abstract

AbstractHigh 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 Mn=43 000 Da). Combined GPC and 31P 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.

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