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The phosphorus analogue of cyclobutadiene, cyclo-P4, can be stabilized as a ligand in the slightly distorted P4Nb pyramid of 1. The photochemical synthesis of 1 was achieved under very mild conditions starting from [Cp*Nb(CO)4] and white phosphorus. The likewise prepared triple-decker complex 2, containing a cyclo-P6 middle “deck”, displays a μ, η3, η3 distortion of the cyclo-P6 ligands as observed for the η5-C5Me4Et analogue.