Polysulfide Coordination Clusters of the Lanthanides

Abstract The reaction of [(DippForm) 2 Ln(thf) 2 ] with an excess of elemental sulfur in toluene resulted in the formation of the trinuclear polysulfide coordination clusters [(DippForm) 3 Ln 3 S 12 ] (Ln=Sm, Yb; DippForm=N,N′‐bis(2,6‐diisopropylphenyl)formamidinate). These are the first f element coordination clusters (Ln n S x ) with a larger polysulfide unit (n and x>2). The formation of the coordination clusters can be rationalized by the reductive cleavage of S 8 with divalent lanthanides.