Observation of a Metastable P‐Heterocyclic Radical by Muonium Addition to a 1,3‐Diphosphacyclobutane‐2,4‐diyl

A 1,3‐diphosphacyclobutane‐2,4‐diyl contains a unique unsaturated cyclic unit, and the presence of radical‐type centers have been expected as a source of functionality. This study demonstrates that the P‐heterocyclic singlet biradical captures muonium (Mu=[μ + e − ]), the light isotope of a hydrogen radical, to generate an observable P‐heterocyclic paramagnetic species. Investigation of a powder sample of 2,4‐bis(2,4,6‐tri‐ t ‐butylphenyl)‐1‐ t ‐butyl‐3‐benzyl‐1,3‐diphosphacyclobutane‐2,4‐diyl using muon (avoided) level‐crossing resonance (μLCR) spectroscopy revealed that muonium adds to the cyclic P 2 C 2 unit. The muon hyperfine coupling constant ( A μ ) indicated that the phosphorus atom bearing the t ‐butyl group trapped muonium to provide a metastable P‐heterocyclic radical involving the ylidic MuP(<)=C moiety. The observed regioselective muonium addition correlates the canonical formula of 1,3‐diphosphacyclobutane‐2,4‐diyl.