Probing Radical Addition to 1-Phosphabutadienes by Employing Muonium as a "Light Isotope" of Hydrogen.

Understanding free radical addition to multiple bonds is important to elucidating the mechanistic details of addition polymerization reactions, albeit the fleeting radical intermediates are very difficult to detect by conventional methodologies. Muon spin spectroscopy (μSR) is a highly sensitive method that can detect radical species at 10 spins (cf. EPR: 10 spins, NMR: 10 spins). Herein, we employ μSR to detect the radical-addition products from three 1-phosphabutadiene monomers, P-analogues of isoprene. We show that muonium (Mu), a "light" H-atom surrogate, adds predominantly at the C position of the P =C -C =C moiety to give unprecedented 1-phosphaallyl radicals as the major products. Our structural assignments are supported by assignment of muon, phosphorus and proton hyperfine coupling constants using DFT-calculations. A minor radical product is also detected that is tentatively assigned to an PC -heterocyclic free radical. On the basis of DFT-predictions, we speculate that its formation may involve initial addition of Mu at the C position followed by electron capture. These studies provide rare insights into the prospective radical (or cationic) polymerization of 1-phosphabutadienes, which have previously been polymerized using anionic initiation.