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Free Radical Reactivity of a Phosphaalkene Explored Through Studies of Radical Isotopologues
Author(s) -
Chandrasena Lalangi,
Samedov Kerim,
McKenzie Iain,
Mozafari Mina,
West Robert,
Gates Derek P.,
Percival Paul W.
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201810967
Subject(s) - muonium , isotopologue , radical , muon , chemistry , reactivity (psychology) , hyperfine structure , photochemistry , molecule , atomic physics , physics , organic chemistry , nuclear physics , pathology , alternative medicine , medicine
Muonium (Mu), an H atom analogue, is employed to probe the addition of free radicals to the P=C bond of a phosphaalkene. Specifically, two unprecedented muoniated free radicals, MesP . −CMu(Me) 2 ( 1 a , minor product) and MesPMu−C . Me 2 ( 1 b , major product), were detected by muon spin spectroscopy (μSR) when a solution of MesP=CMe 2 ( 1 : Mes=2,4,6‐trimethylphenyl) was exposed to a beam of positive muons (μ + ). The μ + serves as a source of Mu (that is, Mu=μ + +e − ). To confirm the identity of the major product 1 b , its spectral features were compared to its isotopologue, MesPH‐C . (Me)CH 2 Mu ( 2 a ). Conveniently, 2 a is the sole product of the reaction of MesPH(CMe=CH 2 ) ( 2 ) with Mu. For all observed radicals, muon, proton, and phosphorus hyperfine coupling constants were determined by μSR and compared to DFT‐calculated values.

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