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Open Chain Polyarsenides of the Lanthanides
Author(s) -
Schoo Christoph,
Köppe Ralf,
Piesch Martin,
Gamer Michael T.,
Konchenko Sergey N.,
Scheer Manfred,
Roesky Peter W.
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201800539
Subject(s) - samarium , lanthanide , intramolecular force , chemistry , divalent , chain (unit) , cobalt , crystallography , coordination sphere , density functional theory , stereochemistry , medicinal chemistry , inorganic chemistry , crystal structure , computational chemistry , organic chemistry , physics , ion , astronomy
The reaction of [(Cp′′′Co) 2 (μ,η 2:2 ‐As 2 ) 2 ] with the decamethylsamarocenes [Cp* 2 Sm(THF) 2 ] or [Cp* 2 Sm], or the bis(tetramethyl‐ n ‐propyl)samarocene [(C 5 Me 4 ( n ‐propyl)) 2 Sm] resulted in the mixed d/f polyarsenides [(Cp′′′Co) 2 As 4 Sm(η 5 ‐C 5 Me 4 R) 2 ] (R=Me, n ‐propyl). They are the first structural representatives of open chain‐like polyarsenides as ligands in the coordination sphere of lanthanides. Their formation can be explained by an intramolecular As–As coupling within the cobalt polyarsenide complex after reduction by the divalent samarium complex. Density functional theory calculations give insight into the structural change of the (As 2 ) 2 unit in [{Cp′′′Co(μ,η 2:2 ‐As 2 )} 2 ] upon reduction.