An Isolable Radical Anion Featuring a 2-Center-3-Electron π-Bond without a Clearly Defined σ-Bond.
Angew Chem Int Ed Engl
; 62(52): e202315555, 2023 Dec 21.
Article
em En
| MEDLINE
| ID: mdl-37942957
ABSTRACT
Featuring an extra electron in the π* antibonding orbital, species with a 2-center-3-electron (2c3e) π bond without an underlying σ bond are scarcely known. Herein, we report the synthesis, isolation and characterization of a radical anion salt [K(18-C-6)]+ {[(HCNDipp)2 Si]2 P2 }â
- (i.e. [K(18-C-6)]+ 3â
- ) (18-C-6=18-crown-6, Dipp=2,6-diisopropylphenyl), in which 3â
- features a perfectly planar Si2 P2 four-membered ring. This species represents the first example of a Si- and P-containing analog of a bicyclo[1.1.0]butane radical anion. The unusual bonding motif of 3â
- was thoroughly investigated via X-ray diffraction crystallography, electron paramagnetic resonance spectroscopy (EPR), and calculations by density functional theory (DFT), which collectively unveiled the existence of a 2c3e π bond between the bridgehead P atoms and no clearly defined supporting P-P σ bond.
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MEDLINE
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En
Ano de publicação:
2023
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Article