- Journal Article
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‐(CF3)2C6H3)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. © 2020 Wiley‐VCH GmbH. Show more
Journal / seriesAngewandte Chemie. International Edition
Pages / Article No.
SubjectCarbenes; Dicarbondiphosphide; Distonic radical cations; Phosphorus; Radicals
Organisational unit03447 - Grützmacher, Hansjörg / Grützmacher, Hansjörg
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