A Strategy for the Synthesis of Phosphorus‐Containing Macrocycles—Ligands for Exceptional Coordination Geometries

The shape of rings to come! The novel synthetic strategy for macrocycles containing differently functionalized ligands is based on a coupling reaction between two alkali-metal-fixed carbanionic centers I and two specifically connected, electrophilic phosphorus centers II (see scheme, Do=donor atom). Twofold PC-bond formation first results in a metallamacrocycle III, which is subsequently converted by protonation into the neutral ring system IV. The formation of unprecedented coordination geometries of CuI and Ni0 centers is shown by the X-ray crystal structures of the complexes V.