Homo- and heterobimetallic transition metal cluster derived from [Cp*Fe(η 5 -E 5 )] (E = P, As) - unprecedented structural motifs of the resulting polypnictogen ligands.

A general synthetic procedure to neutral homo- and heterobimetallic cage compounds exhibiting various structural motifs of the polypnictogen ligands starting from [Cp*Fe(η 5 -E 5 )] (E = P (1), As (2); Cp* = C 5 Me 5 ) is reported. The impact of the implemented transition metal precursors {Cp'''M} (M = Cr, Mn, Fe, Ni; Cp''' = 1,2,4- t Bu 3 C 5 H 2 ) emphasises the variability of the isolated complexes exhibiting a broad variety of structural motifs of the pnictogen ligands. Spectroscopic, crystallographic, and theoretical investigations provide insight into the structure of the partially unprecedented polypnictogen ligands.