Alkali-metal phosphanides can be embedded into a [3]ferrocenophane scaffold giving rise to bicyclic ferrocenophanes [MFe(C5H4PtBu)2P] (M = Li, Na, K). Coordination of the alkali-metal ions takes place via the terminal phosphorus atoms adopting a puckered P3M four-membered ring. All compounds were characterized via single-crystal X-ray diffraction and multinuclear NMR spectroscopy (1H, 31P, 7Li), whereas 13C NMR data could only be recorded for the Li derivative, owing to the limited solubility of its heavier congeners ...