The Triplet Hydroxyl Radical Complex of Phosphorus Monoxide.
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.
['Chu|Xianxu|X|', 'Qian|Weiyu|W|', 'Lu|Bo|B|', 'Wang|Lina|L|http://orcid.org/0000-0002-9194-3527', 'Qin|Jie|J|', 'Li|Jun|J|', 'Rauhut|Guntram|G|', 'Trabelsi|Tarek|T|', 'Francisco|Joseph S|JS|http://orcid.org/0000-0002-5461-1486', 'Zeng|Xiaoqing|X|http://orcid.org/0000-0003-4611-2094']
radicals complexes IR spectroscopy hydrogen bonds phosphorus oxides