Threefold cross-linked polystyrene-triphenylphosphane hybrids: mono-P-ligating behavior and catalytic applications for aryl chloride cross-coupling and C(sp(3))-H borylation.

Covalently bound polystyrene-phosphane hybrids were prepared by a method based on radical emulsion polymerization of styrenes in the presence of a tris(p-vinylphenyl)phosphane cross-linker. These hybrids favor mono-P-ligation to transition-metal complexes and are useful for challenging catalysis, such as Pd-catalyzed CC/CN couplings with unactivated chloroarenes and Ir- or Rh-catalyzed C(sp(3) )H borylations.