Synthesis of a Molecule with Five Different Adjacent Pnictogens

The first molecular compound with all five pnictogens was obtained by a multi‐step reaction. Lithiation of the (bisamido)diazadiarsetidine (tBuNAs)(2)(tBuNH)(2) in aliphatic solvents leads to the dimeric metallated species [(tBuNAs)(2)(tBuNLi)(2)](2) (1(2)). Upon reactions with AsCl(3), SbCl(3) and BiCl(3) the polycyclic compounds [(tBuNAs)(2)(tBuN)(2)]PnCl (Pn=As (2), Sb (3), Bi (4)) can be obtained. Conversion of 2–4 with [tBu(2)SbP(tBu)Li(OEt(2))](2) leads to the remarkable interpnictogens [(tBuNAs)(2)(tBuN)(2)]PnP(tBu)SbtBu(2) (Pn=As (5), Sb (6), Bi (7)), whereby 7 is the first example of a molecule containing all five Group 15 elements. The compound with adjacent AsNBiPSb‐chains is surprisingly stable and does not show high sensibility against light as the labile Bi−P bond might suggest.