Molecular Polyarsenides of the Rare‐Earth Elements |
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| Authors: | Dr. Nicholas Arleth Dr. Michael T. Gamer Dr. Ralf Köppe Prof. Dr. Sergey N. Konchenko Martin Fleischmann Prof. Dr. Manfred Scheer Prof. Dr. Peter W. Roesky |
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| Affiliation: | 1. Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Karlsruhe, Germany;2. Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk, Russia;3. Novosibirsk State University, Novosibirsk, Russia;4. Institute of Inorganic Chemistry, University of Regensburg, Regensburg, Germany |
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| Abstract: | Reduction of [Cp*Fe(η5‐As5)] with [Cp′′2Sm(thf)] (Cp′′=η5‐1,3‐(tBu)2C5H3) under various conditions led to [(Cp′′2Sm)(μ,η4:η4‐As4)(Cp*Fe)] and [(Cp′′2Sm)2As7(Cp*Fe)]. Both compounds are the first polyarsenides of the rare‐earth metals. [(Cp′′2Sm)(μ,η4:η4‐As4)(Cp*Fe)] is also the first d/f‐triple decker sandwich complex with a purely inorganic planar middle deck. The central As42? unit is isolobal with the 6π‐aromatic cyclobutadiene dianion (CH)42?. [(Cp′′2Sm)2As7(Cp*Fe)] contains an As73? 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,η4:η4‐As4)(Cp*Fe)] was estimated to be in between an As?As single bond and a formally aromatic As42? system. |
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| Keywords: | arsenides lanthanides polyarsenide samarium triple-decker sandwich complex |
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