A silica-supported tripod triarylphosphane (Silica-3p-TPP), containing a triphenylphosphanetype core tripodally immobilized on the silica surface, allows rhodium-and iridium-catalyzed CA C H T U N G T R E N N U N G (sp 3) À H borylations of amide, urea and alkylpyridine derivatives. The 31 P CP/MAS NMR studies for the coordination behavior of the tripod phosphane towards a rhodium complex indicate efficient site isolation of the each phosphane center, allowing independent mono-P-coordination to the metal center.