Dang Anh N, Rogalski Maya H, Peterman Dean R, Mincher Bruce J, Mezyk Stephen P
California State University at Long Beach, Department of Chemistry and Biochemistry, 1250 N. Bellflower Blvd., Long Beach, CA, 90840, USA.
Idaho National Laboratory, Center for Radiation Chemistry Research, PO Box 1625, Idaho Falls, ID, 83415, USA.
Phys Chem Chem Phys. 2024 Sep 11;26(35):23003-23009. doi: 10.1039/d4cp00751d.
The reactivity of the nitrate radical (NO˙) with organophosphorus and amidic actinide and lanthanide complexing agents of interest to nuclear solvent extraction applications was measured, resulting in the first-ever reported bimolecular rate constants for this radicals' reactions in dodecane solution. The order of reactivity for neutral organophosphorus compounds showed faster rate constants with increasing electron density on the phosphoryl phosphorus atom, indicating an increasing facility for electron abstraction reactions occurring in addition to H-atom abstraction from the ligand alkane chains. The only acidic organophosphorus compound investigated, HEH[EHP], showed low reactivity with the NO˙ radical, attributed to its dimerization in this non-polar solvent. Amide ligand reaction rates were faster than for organophosphorus molecules, suggesting more facile H-atom abstraction from carbonyl activated methylene and amyl groups. While all rate constants were slower than the diffusion-limited rate they were still rapid enough to result in significant oxidation of solvent extraction ligands in dodecane solution.
测量了硝酸根自由基（NO˙）与核溶剂萃取应用中感兴趣的有机磷以及酰胺类锕系和镧系络合剂的反应活性，得出了该自由基在十二烷溶液中反应的双分子速率常数，这是有史以来首次报道。中性有机磷化合物的反应活性顺序表明，随着磷酰基磷原子上电子密度的增加，速率常数加快，这表明除了从配体烷烃链上夺取氢原子外，发生电子夺取反应的能力也在增加。所研究的唯一酸性有机磷化合物HEH[EHP]与NO˙自由基的反应活性较低，这归因于其在这种非极性溶剂中的二聚作用。酰胺配体的反应速率比有机磷分子快，这表明从羰基活化的亚甲基和戊基夺取氢原子更容易。虽然所有速率常数都比扩散限制速率慢，但它们仍然足够快，足以导致十二烷溶液中的溶剂萃取配体发生显著氧化。
