TY  - JOUR
A1  - Bock, Hans
A1  - Arad, Claudia
A1  - Näther, Christian
A1  - Göbel, Ilka
A1  - John, Andreas
T1  - Strukturen ladungsgestörter oder räumlich überfüllter Moleküle, 108 [1] Strukturänderungen bei der Zweifach-Reduktion von Tetraphenyl-p-chinodimethan zu seinem Dianion
T1  - Structures of Charge-Perturbed or Sterically Overcrowded Molecules, 108 [1] Structural Changes of Tetraphenyl-p-quinodim ethane on Twofold Reduction to its Dianion
T2  - Zeitschrift für Naturforschung, B
N2  - The two-electron reduction of tetraphenyl-p-quinodimethane M via its radical anion M⊖ to its dianion M⊖⊖ is explored both by cyclovoltammetry and ESR/ENDOR spectroscopy. Contact of the diglyme solution with added 15-crown-5 under aprotic conditions with a sodium metal mirror yields black crystals of a solvent-separated contact ion triple [M⊖⊖][Na⊕(OCH2CH2)5(H3CO(CH2CH2O)2CH3)]2. The two-electron-insertion into the pquinodimethane derivative R2C⊖=C(HC=CH)2C=CR2 changes its structure drastically to that of a twofold carbanion substituted benzene, R2C⊖ -(C6H4)- ⊖CR2. MNDO calculations provide a rationale for both the tremendous solvation of a Na⊕ center coordinated to seven oxygen centers of 15-crown-5 and of one diglyme molecule and the structural changes as well as the charge distribution in the unique Tetraphenyl-p-quinodimethane dianion (H5C6)2C⊖-(C6H4)- ⊖C(C6H5)2, in which the two negative charges are largely localized at the carbanion center of the benzene -substituents.
KW  - Crystal Structure
KW  - Tetraphenyl-p-quinodimethane Dianion
KW  - Cyclovoltammetry
KW  - ESR/ENDOR Measurements
KW  - MNDO Calculations
Y1  - 2023
UR  - http://publikationen.ub.uni-frankfurt.de/frontdoor/index/index/docId/74204
UR  - https://nbn-resolving.org/urn:nbn:de:hebis:30:3-742045
SN  - 1865-7117
SN  - 0932-0776
VL  - 51
IS  - 10
SP  - 1391
EP  - 1399
PB  - Verlag der Zeitschrift für Naturforschung
CY  - Tübingen
ER  -