Molecular Polyarsenides of the Rare-Earth Elements

Arleth, Nicholas and Gamer, Michael T. and Koeppe, Ralf and Konchenko, Sergey N. and Fleischmann, Martin and Scheer, Manfred and Roesky, Peter W. (2016) Molecular Polyarsenides of the Rare-Earth Elements. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 55 (4). pp. 1557-1560. ISSN 1433-7851, 1521-3773

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Abstract

Reduction of [Cp*Fe(eta(5)-As-5)] with [Cp-2 '' Sm(thf)]/(Cp '' = eta(5)-1,3-(tBu)(2)C5H3) under various conditions led to [(Cp-2 '' Sm)(mu,eta(4):eta(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)(mu,eta(4) :eta(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 6p-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)(mu,eta(4) :eta(4)-As-4)(Cp*Fe)] was estimated to be in between an As-As single bond and a formally aromatic As-4(2-) system.

Item Type: Article
Uncontrolled Keywords: P-4 ACTIVATION; BUILDING-BLOCK; COMPLEXES; LIGANDS; CRYSTAL; PHOSPHORUS; REACTIVITY; ANIONS; BOND; SAMARIUM(II); arsenides; lanthanides; polyarsenide; samarium; triple-decker sandwich complex
Subjects: 500 Science > 540 Chemistry & allied sciences
Divisions: Chemistry and Pharmacy > Institut für Anorganische Chemie
Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer
Depositing User: Dr. Gernot Deinzer
Date Deposited: 15 Mar 2019 08:59
Last Modified: 15 Mar 2019 08:59
URI: https://pred.uni-regensburg.de/id/eprint/2529

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