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Updated: Dec 5, 2025

Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus
Published on: October 3, 2014
The Triplet Hydroxyl Radical Complex of Phosphorus Monoxide
Xianxu Chu1, Weiyu Qian1, Bo Lu1
1College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.
Abstract:
Phosphorus monoxide (. PO) is a key intermediate in phosphorus chemistry, and its association with the hydroxyl radical (. OH) to yield metaphosphorous acid (cis-HOPO) contributes to the chemiluminescence in the combustion of phosphines. When photolyzing cis-HOPO in an Ar-matrix at 2.8 K, the simplest dioxophosphorane HPO2 and an elusive hydroxyl radical complex (HRC) of . PO form. This prototypical radical-radical complex reforms into cis-HOPO at above 12.0 K by overcoming a barrier of 0.28±0.02 kcal mol-1 . The vibrational spectra of this HRC and its D- and 18 O-isotopologues suggest a structure of . OH⋅⋅⋅OP. , for which a triplet spin multiplicity with a binding energy of -3.20 kcal mol-1 has been computed at the UCCSD(T)-F12a/aug-cc-pVTZ level.
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