A Germapyramidane Switches Between 3D Cluster and 2D Cyclic Structures in Single-Electron Steps
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2022-11-21
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Journal Article
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yes
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Abstract
Reaction 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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published
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61 (47)
Pages / Article No.
e202211749
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Wiley-VCH
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Subject
Aromaticity; Cluster Compounds; Density Functional Calculations; Main-Group Elements; Redox Chemistry
Organisational unit
09654 - Mougel, Victor / Mougel, Victor
03447 - Grützmacher, Hansjörg (emeritus) / Grützmacher, Hansjörg (emeritus)
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181966 - Coordinated radicals and catalyzed dehydrogenation reactions II (SNF)
ETH-36 17-2 - Phosphaethynolate as building block for Heterocycles and Metal Phosphides (ETHZ)
ETH-36 17-2 - Phosphaethynolate as building block for Heterocycles and Metal Phosphides (ETHZ)