Synthesis of Unprecedented 4d/4f-Polypnictogens.

A series of 4d/4f-polyarsenides, -polyarsines and -polystibines was obtained by reduction of the Mo-pnictide precursor complexes [{Cpt Mo(CO)2 }2 (μ,η2:2 -E2 )] (E=As, Sb; Cpt =tBu substituted cyclopentadienyl) with two different divalent samarocenes [Cp*2 Sm] and [(CpMe4nPr )2 Sm]. For the reductive conversion of the Mo-stibide only one product was isolated, featuring a planar tetrastibacyclobutadiene moiety as an unprecedented ligand for organometallic compounds. For the corresponding Mo-arsenide a tetraarsacyclobutadiene and a second species with a side-on coordinated As2 2- anion was isolated. The latter can be considered as reaction intermediate for the formation of the tetraarsacyclobutadiene.