Exploring the Modularity of Triphenylphosphine-Containing Polymers as Diverse Transition Metal Catalysts

Polymers provide a versatile platform for tuning the local environment of transition metal catalysts, yet most systems are optimized for a single metal or reaction class. Here, we demonstrate that a single copolymer of triphenylphosphine acrylamide (TPPAm) and <i>N,N</i>-dimethylacrylamide (DMA) can be modularly complexed with transition metals to access multiple unique catalysts, each capable of mediating distinct chemical transformations. Specifically, three metal-polymer catalysts were evaluated in transformations characteristic of each metal center, including Sonogashira cross-coupling (Pd), allylic amination (Pt), and 1,4-conjugate addition (Rh). Phosphine coordination was required for catalysis, as indicated by minimal reactivity of metal-treated, nonfunctional polymer controls. Across all systems, the polymer-supported catalysts exhibited reactivity comparable to or exceeding that of small-molecule analogues with improved operational stability observed for select metal centers under benchtop conditions. Collectively, these results establish TPPAm-containing polymers as a generalizable scaffold for polymer-supported catalysis across multiple metal centers and provide a foundation for systematically probing how metal identity and polymer structure jointly govern catalytic behavior.