Polymer networks functionalized with low‐valent phosphorus cations

Abstract

AbstractIn this work, we show that polymer networks composed of tertiary alkyl phosphines can be cleanly functionalized with phosphino‐phosphonium or triphosphenium cations. Methods for functionalizing the polymers range from halide abstraction of commercially available reagents, to ligand exchange from simple to make reported compounds, and finally, macromolecular ligand design guided by observations made at the molecular level to accommodate the formation of kinetically favored triphosphenium cation functionalized networks. The synthesis, comprehensive characterization, and comparison of the new polymers to molecular analogues is outlined. It is shown the addition of the low valent phosphorus centers to the polymer network has the effect of tuning material physical properties.