Abstract The synthesis of π-acceptor ligands of the type PAr x R 3− x (x= 0− 2; R= pyrrolyl, indolyl, carbazolyl; Ar= aryl)(1− 8, 10, 12, 13) and P (pyrrolyl) 2 (carbazolyl)(11) is described. These ligands can be prepared in good to excellent yields by treatment of the corresponding free heterocyclic amines with phosphorus chlorides in the presence of base. The utilization of pyrrolyl-, indolyl-, and carbazolylphosphanes in the rhodium-catalyzed hydroformylation ...