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Molecular Polyarsenides of the Rare‐Earth Elements
Author(s) -
Arleth Nicholas,
Gamer Michael T.,
Köppe Ralf,
Konchenko Sergey N.,
Fleischmann Martin,
Scheer Manfred,
Roesky Peter W.
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201509749
Subject(s) - astrobiology , rare earth , earth (classical element) , geology , earth science , biology , physics , astronomy
Reduction of [Cp*Fe(η 5 ‐As 5 )] with [Cp′′ 2 Sm(thf)] (Cp′′=η 5 ‐1,3‐( t Bu) 2 C 5 H 3 ) under various conditions led to [(Cp′′ 2 Sm)(μ,η 4 :η 4 ‐As 4 )(Cp*Fe)] and [(Cp′′ 2 Sm) 2 As 7 (Cp*Fe)]. Both compounds are the first polyarsenides of the rare‐earth metals. [(Cp′′ 2 Sm)(μ,η 4 :η 4 ‐As 4 )(Cp*Fe)] is also the first d/f‐triple decker sandwich complex with a purely inorganic planar middle deck. The central As 4 2− unit is isolobal with the 6π‐aromatic cyclobutadiene dianion (CH) 4 2− . [(Cp′′ 2 Sm) 2 As 7 (Cp*Fe)] contains an As 7 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 As 4 ligand in [(Cp′′ 2 Sm)(μ,η 4 :η 4 ‐As 4 )(Cp*Fe)] was estimated to be in between an As−As single bond and a formally aromatic As 4 2− system.