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An Isolable Heteroleptic Diarylphosphinyl Radical

Yizhen Chen, Mengyuan Wu, Dongmin Wang, Ningning Yuan, Lei Xu, Gengwen Tan

2023Organometallics11 citationsDOI

Abstract

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.

Topics & Concepts

ChemistryRadicalReactivity (psychology)Steric effectsSubstituentElectron paramagnetic resonancePhotochemistryDensity functional theorySpectroscopyComputational chemistrySpin densityNuclear magnetic resonance spectroscopyStereochemistryOrganic chemistryNuclear magnetic resonanceCondensed matter physicsMedicineAlternative medicinePhysicsPathologyQuantum mechanicsSynthesis and characterization of novel inorganic/organometallic compoundsOrganometallic Complex Synthesis and CatalysisOrganoboron and organosilicon chemistry
An Isolable Heteroleptic Diarylphosphinyl Radical | Litcius