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 P2 C2 unit. The muon hyperfine coupling constant (Aμ ) 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.