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A Room‐Temperature Stable Distonic Radical Cation
Author(s) -
Chen Xiaodan,
Liu Liu Leo,
Liu Shihua,
Grützmacher Hansjörg,
Li Zhongshu
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202011677
Subject(s) - electron paramagnetic resonance , chemistry , intramolecular force , matrix isolation , crystallography , density functional theory , spectroscopy , radical ion , photochemistry , radical , ion , stereochemistry , computational chemistry , infrared spectroscopy , nuclear magnetic resonance , organic chemistry , physics , quantum mechanics
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 β‐distonic radical cation salt 3 .+ (BARF) (BARF=[B(3,5‐(CF 3 ) 2 C 6 H 3 ) 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 (0.74 a.u.) and a cationic charge located predominantly at the four‐coordinate phosphorus atom (1.53 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.