A silica-supported triptycene-type phosphine, Silica-TRIP, comprising a 9-phospha-10- silatriptycene (TRIP) and silica gel as a P-coordination center and a solid support, respectively, was synthesized and structurally characterized by nitrogen absorption measurements and solid-state CP/MAS NMR spectroscopy. Silica-TRIP exhibited a mono-P- ligating feature toward a Pd (II) complex, resulting in selective formation of a 1/1 Pd–P ...