Abstract
AbstractReaction of the imidazolium‐substituted iphosphate‐diide, (Ipr)2C2P2 (IDP), with GeCl2 ⋅ 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‐C4H4)]. [1]2+ undergoes two reversible one‐electron reductions, which yield the radical cation [2]⋅+ and the neutral GeII species 3. Both [2]⋅+ 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.
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