CuI click catalysis with cooperative noninnocent pyridylphosphine ligands

► Synthesis and coordination chemistry with Cu(I) of new bidentate P,N-ligand. ► First description of noninnocence in PN-ligand backbone. ► Molecular structure of dimeric copper(I)-complex of new P,N-ligand. ► Cooperative catalysis in click reaction with two all-inclusive Cu(I) species.