Related Experiment Video
Updated: Feb 7, 2026

Free Radicals in Chemical Biology: from Chemical Behavior to Biomarker Development
Published on: April 15, 2013
The Simplest Phosphinylperoxy Radical and Its Isomers in the Photochemical Phosphorus-Hydrogen-Oxygen Network
Junjie Jiang1, Yixin Guo1, Longtian Huang1
1Department of Chemistry, Advanced Institute of Future Energy, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, China.
Abstract:
The oxidation of phosphine (PH3) plays an important role in the photochemical phosphorus-hydrogen-oxygen network of the Earth's atmosphere. The phosphinyl radical (•PH2) is a key intermediate in the photochemistry of PH3, and its reactions with O2 yield phosphorus oxyacids as stable reservoirs via the intermediacy of yet elusive radicals. Herein, we report the identification of the simplest phosphinylperoxy radical H2POO• in gas phase reaction between •PH2 and O2. The characterization of H2POO• with matrix-isolation IR and UV-vis spectroscopy is supported by D- and 18O-isotope labeling experiments and quantum chemical calculations. Upon photoexcitation at 410 nm, the matrix-isolated H2POO• undergoes successive hydrogen-migration to form two isomers HP(O)OH• and •P(OH)2. Further UV-irradiation at 365 nm causes decomposition to yield the water complex of phosphorus monoxide (•PO), which can be photolytically converted to metaphosphorous acid (HOPO). The disclosed photochemistry of these novel phosphorus-bearing molecules helps in understanding the photochemical network of PH3 in the atmospheric and interstellar phosphorus chemistry.
Related Concept Videos
Hydrogen Bonds
Hydrogen Bonds Control the World!
Because hydrogen has very weak electronegativity when it binds with a strongly electronegative atom, such as oxygen or nitrogen, electrons in the bond are unequally shared....
Hydrogen Bonds
Constitutional Isomers of Alkanes
The linear isomer of an alkane is prefixed by the term “n”; hence a linear isomer of pentane is known as n-pentane. Based on the type of branching, some of the...
The Phosphorus Cycle
Network Covalent Solids
To break or to melt a covalent network solid, covalent bonds must be broken. Because covalent bonds are relatively strong, covalent network solids are typically...
Protein Networks
These interactions can be represented through maps depicting protein-protein interaction networks, represented as nodes and edges. Nodes are circles that are representative of a protein,...

