An Isolable Heteroleptic Diarylphosphinyl Radical

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Diarylphosphinyl radicals [Ar 2 P] • have been known as transient species for over 50 years, but their isolation in the condensed form has not been realized until now. In this work, we report the synthesis and structural and spectroscopic characterizations of the first isolable heteroleptic diarylphosphinyl radical 3 supported by a sterically congested hydrindacene substituent. Electron paramagnetic resonance spectroscopy and density functional theory calculations reveal that the spin density mainly resides at the phosphorus center. The reactivity of 3 toward C 2 Cl 6 and n Bu 3 SnH was investigated, affording diarylchlorophosphine and diarylphosphine, respectively, revealing its phosphorus-centered radical nature.