A Room-Temperature Stable Distonic Radical Cation.
Angew Chem Int Ed Engl
; 59(52): 23830-23835, 2020 Dec 21.
Article
em En
| MEDLINE
| ID: mdl-32914528
ABSTRACT
Distonic radical cations (DRCs) with spatially separated charge and radical sites have, so far, largely been observed by gas-phase mass spectrometry and/or matrix isolation spectroscopy work. Herein, we disclose the isolation of a crystalline dicarbondiphosphide-based ß-distonic radical cation salt 3.+ (BARF) (BARF=[B(3,5-(CF3 )2 C6 H3 )4 )]- ) stable at room temperature and formed by a one-electron-oxidation-induced intramolecular skeletal rearrangement reaction. Such a species has been validated by electron paramagnetic resonance (EPR) spectroscopy, single-crystal X-ray diffraction, UV/Vis spectroscopy and density functional theory (DFT) calculations. Compound 3.+ (BARF) exhibits a large majority of spin density at a two-coordinate phosphorus atom (0.74â
a.u.) and a cationic charge located predominantly at the four-coordinate phosphorus atom (1.53â
a.u.), which are separated by one carbon atom. This species represents an isolable entity of a phosphorus radical cation that is the closest to a genuine phosphorus DRC to date.
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Base de dados:
MEDLINE
Idioma:
En
Ano de publicação:
2020
Tipo de documento:
Article
País de afiliação:
China