Well-defined Pt(0) heterogeneous hydrosilylation catalysts supported by a surface bound phosphenium ligand

Single atom, low valent transition metals are important for heterogeneous catalysis but are challenging to generate and stabilize in a well-defined manner. Herein, we explored the functionalization of silica with well-defined N-heterocyclic phosphenium (NHP) ions to heterogenize low-valent metals. The surface electrostatically bound [NHP]⁺ ions coordinate to Pt(0) precursors, resulting in well-defined, chemisorbed [(NHP)Pt(0)L_n]⁺ sites. The resulting materials catalyze the hydrosilylation of alkynes and exhibit activities and selectivities that rival the current industry standard homogeneous catalysts. The catalysts leach Pt, limiting their recyclability; however, recycling studies support that the high regioselectivities arise from heterogeneous sites and Pt particles do not form on the surface. We suspect that this phosphenium-based immobilization strategy will result in stable, tunable, low valent heterogeneous transition metal catalysts in a wider array of catalytic reactions.