TY  - JOUR
A1  - Bock, Hans
A1  - John, Andreas
A1  - Näther, Christian
A1  - Havlas, Zdenek
T1  - Elektronentransfer und Ionenpaar-Bildung, 34 [1-3]. Einkristallstruktur des Solvens-separierten Radikalionenpaares [9,9′-Bianthryle·⊖][Na⊕(DME)3]
T1  - Electron transfer and ion pair formation, 34 [1-3]. Single crystal structure of the solvent-separated ion pair [9,9′-bianthryle·⊖][Na⊕(DME)3]
T2  - Zeitschrift für Naturforschung, B
N2  - The one-electron transfer to large π-delocalized hydrocarbons provides an interesting possibility to crystallize solvent-separated ion-pair salts containing optimally solvated cations. Accordingly, the reduction of 9.9′-bianthryl in aprotic 1.2-dimethoxyethane (DME) solution at a sodium metal mirror allows to grow dark blue, brick-like crystals of its radical anion and threefold DME-solvated sodium cation. The structure of the radical anion is very similar to that recently published for the neutral molecule. According to AM 1 enthalpy hypersurface calculations based on the structural data, the torsion angle between 60° and 120° is determined by the lattice packing and the negative charge is -π-delocalized predominantly within only one anthracene subunit. The counter cation [Na⊕(DME)3], reported only three times so far, shows a sixfold propeller-like coordination of approximate D3 skeletal symmetry with contact distances Na⊕···O between 232 and 243 pm and angles ≮ONa⊕O varying between 69° and 159°. Due to the small repulsion between the chelating DME molecules, the isodesmically calculated Na⊕ solvation enthalpy is more negative than that of the analogous tetrahydrofuran complex [Na⊕(THF)6] - as confirmed by the laboratory experience that salts of less stable anions are preferentially crystallized from a strongly cation solvating DME solution.
KW  - One-Electron Reduction of 9,9′-Bianthryl
KW  - Solvent-Separated Radical Ion Pair
KW  - Optimally Solvated Sodium Cation
KW  - Single Crystal Structure
Y1  - 2014
UR  - http://publikationen.ub.uni-frankfurt.de/frontdoor/index/index/docId/81656
UR  - https://nbn-resolving.org/urn:nbn:de:hebis:30:3-816569
SN  - 1865-7117
SN  - 0932-0776
VL  - 49.1994
IS  - 10
SP  - 1339
EP  - 1347
PB  - Verlag der Zeitschrift für Naturforschung
CY  - Tübingen
ER  -