Polyphosphorus Ligand Complexes of Coinage Metals for Multiple Capturing of Intact P ₄ Tetrahedra

Abstract Two‐ and three‐component self‐assembly reactions of [Cp R Fe(η 5 ‐P 5 )] (Cp R = C 5 (CH 3 ) 5 (Cp*, 1a ), C 5 (4‐EtC 6 H 4 ) 5 ) (Cp PEt , 1b )) with the coinage metal salts [Cu(CH 3 CN) 4 ][SbF 6 ] or AgSbF 6 were investigated to study the prerequisites for the potential coordination of white phosphorus by using a sterically encumbered Cp R ligand and noncoordinating anions. In the self‐assembly reactions with white phosphorus, either 0D or 1D coordination complexes are formed, all of which feature coordinated intact P 4 tetrahedra and thus comprise an unprecedented class of mixed polyphosphorus ligand complexes capable of complete release of P 4 in solution confirmed by NMR studies. The bulkiness of the used Cp R ligand and the correctly chosen solvent allowed for obtaining more beneficial structural motifs, the first discrete tetra‐ and penta‐coordinated cyclo ‐P 5 ligand complexes, that provide the maximal content of coordinated P 4 molecules per species known so far. All products are characterized by single‐crystal X‐ray diffraction, NMR spectroscopy, and mass spectrometry.