A Germapyramidane Switches Between 3D Cluster and 2D Cyclic Structures in Single-Electron Steps.
Angew Chem Int Ed Engl
; 61(47): e202211749, 2022 Nov 21.
Article
em En
| MEDLINE
| ID: mdl-36152009
ABSTRACT
Reaction of the imidazolium-substituted iphosphate-diide, (Ipr)2 C2 P2 (IDP), with GeCl2 â
dioxane and KBArF24 [(BarF24 )- =tetrakis[(3,5-trifluoromethyl)phenyl]borate)] afforded the dicationic spherical-aromatic nido-cluster [Ge(η4 -IDP)]2+ ([1]2+ ) (Ipr=1,3-bis(2,6-diisopropylphenyl)imidazolium-2-ylidene). This complex is a rare heavy analogue of the elusive pyramidane [C(η4 -C4 H4 )]. [1]2+ undergoes two reversible one-electron reductions, which yield the radical cation [2]â
+ and the neutral GeII species 3. Both [2]â
+ and 3 rearrange in solution forming the 2D aromatic and planar imidazolium-substituted digermolide [4]2+ and germole-diide 5, respectively. Both planar species can be oxidized back to [1]2+ using AgSbF6 . These redox-isomerizations correspond to the fundamental transformation of a 3D aromatic cluster into a 2D aromatic ring compound upon reduction and vice versa. The mechanism of these reactions was elucidated using DFT calculations and cyclic voltammetry experiments.
Texto completo:
1
Base de dados:
MEDLINE
Idioma:
En
Ano de publicação:
2022
Tipo de documento:
Article