Supramolecular Construction of Bidentate Ligands Through Self‐assembly by Hydrogen Bonding

The phosphine ligands presented in this chapter can form hydrogen bonding with an appropriate second ligand in the coordination sphere of a transition metal. By this a classical bidentate ligand with a covalent backbone can be emulated. The second ligand can be either a tautomeric form of the ligand itself or, similar to the A–T base pairing in the DNA, a ligand with a specific complementary interaction side. Catalysts based on these ligand systems could be successfully applied in various reactions such as hydroformylation, asymmetric hydrogenation, hydrocyanation, allylic substitution, or hydration of alkynes or nitriles.