Molecular Polyarsenides of the Rare‐Earth Elements

Abstract

Reduction of [Cp*Fe(η(5)-As5)] with [Cp''2Sm(thf)] (Cp''=η(5)-1,3-(tBu)2C5H3) under various conditions led to [(Cp''2Sm)(μ,η(4):η(4)-As4)(Cp*Fe)] and [(Cp''2Sm)2As7(Cp*Fe)]. Both compounds are the first polyarsenides of the rare-earth metals. [(Cp''2Sm)(μ,η(4):η(4)-As4)(Cp*Fe)] is also the first d/f-triple decker sandwich complex with a purely inorganic planar middle deck. The central As4(2-) unit is isolobal with the 6π-aromatic cyclobutadiene dianion (CH)4(2-). [(Cp''2Sm)2As7(Cp*Fe)] contains an As7(3-) cage, which has a norbornadiene-like structure with two short As-As bonds in the scaffold. DFT calculations confirm all the structural observations. The As-As bond order inside the cyclo As4 ligand in [(Cp''2Sm)(μ,η(4):η(4)-As4)(Cp*Fe)] was estimated to be in between an As-As single bond and a formally aromatic As4(2-) system.