Molecular Polyarsenides of the Rare-Earth Elements

Nicholas Arleth, Michael T. Gamer, Ralf Köppe, Sergey N. Konchenko, Martin Fleischmann, Manfred Scheer, Peter W. Roesky

Research output: Contribution to journalArticlepeer-review

28 Citations (Scopus)

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,η44-As4)(Cp∗Fe)] and [(Cp″2Sm)2As7-(Cp∗Fe)]. Both compounds are the first polyarsenides of the rare-earth metals. [(Cp″2Sm)(μ,η44-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,η44-As4)(Cp∗Fe)] was estimated to be in between an As-As single bond and a formally aromatic As42- system.

Original languageEnglish
Pages (from-to)1557-1560
Number of pages4
JournalAngewandte Chemie - International Edition
Volume55
Issue number4
DOIs
Publication statusPublished - 22 Jan 2016

Keywords

  • arsenides
  • lanthanides
  • polyarsenide
  • samarium
  • triple-decker sandwich complex

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