“…For the heavier alkaline‐earth metals, bis(trimethylsilyl)amides [(thf) 2 Ae{N(SiMe 3 ) 2 } 2 ] (Ae=Ca, Sr, Ba) were used as precursors. However, the lower basicity/reactivity of amido ligands [(SiMe 3 ) 2 N] − compared to alkyl ligands hampered the isolation of “homoleptic” phosphandiides, and hence mixed phosphanide–phosphandiide complexes [{Ae{μ 4 ‐PSiR 3 }} 4 {(thf) x Ae{μ 2 ‐PHSiR 3 } 2 } 2 ] (Ae=Ca, R= t Bu, x =1, 38 ; Ae=Sr, R= t Bu, x =1, 39 ; Ae=Sr, R= i Pr, x =2, 40 ; Ae=Ba, R= t Bu, x =1, 41 ) were obtained (Scheme ) . These reactions are more intricate and also led to phosphanide complexes of the type [(thf) 4 Ae{PH(SiR 3 )} 2 ] or heteroleptic phosphanide‐silylamide “intermediates”, for example, [(thf) 2 Ae{μ‐PHR}{N(SiMe 3 ) 2 }] 2 .…”