Free Radical Reactivity of a Phosphaalkene Explored Through Studies of Radical Isotopologues

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^. Me₂ (1 b, major product), were detected by muon spin spectroscopy (μSR) when a solution of MesP=CMe₂ (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)CH₂ Mu (2 a). Conveniently, 2 a is the sole product of the reaction of MesPH(CMe=CH₂ ) (2) with Mu. For all observed radicals, muon, proton, and phosphorus hyperfine coupling constants were determined by μSR and compared to DFT-calculated values.